KR101162944B1 - Systems, methods, and catalysts for producing a crude product - Google Patents

Abstract

Contacting the crude oil feed with one or more catalysts yields a final product comprising the crude oil product. The crude product is present in a liquid mixture at 25 ° C., 0.101 MPa. One or more other properties of the crude oil product are changeable by at least 10% for each characteristic of the crude oil feed.

Description

SYSTEMS, METHODS AND CATALYSTS FOR PREPARING CRUDE PRODUCTS {SYSTEMS, METHODS, AND CATALYSTS FOR PRODUCING A CRUDE PRODUCT}

Generally, the present invention relates to systems, methods and catalysts for processing crude oil feeds. The present invention also relates to compositions which can be prepared using such systems, methods and catalysts. More specifically, the embodiments described herein relate to systems, methods and catalysts for converting a crude oil feed to a final product, wherein the final product is a liquid mixture at 25 ° C., 0.101 MPa. Crude oil products that are present and have one or more characteristics that vary with respect to each characteristic of the crude oil feed.

Crude oil that has one or more unsuitable characteristics that makes it impossible to transport it economically or cannot be processed using conventional facilities is commonly referred to as "lower crude oil".

Lower crude oil may include acidic components that contribute to the total acid number of the crude feed. Lower crude oil with a relatively high TAN causes corrosion of the metal fittings during its transport and / or processing. Removing acidic components from lower crude oil involves the process of neutralizing the acidic components with various bases. Alternatively, corrosion resistant metals may be used in the conveying device and / or the processing device. Since the use of corrosion resistant metals, in many cases, involves significant expense, the use of corrosion resistant metals in existing installations is undesirable. Another method for preventing corrosion involves the addition of a corrosion inhibitor to the lower crude oil prior to transfer and / or treatment of the lower crude oil. The use of corrosion inhibitors can adversely affect the quality of the devices and / or the products used to process the crude oil.

Lower crude oil, in many cases, contains a relatively high level of residue. Such high residue levels make transfer and / or processing with existing installations difficult and costly.

Lower crude oils in many cases contain organic bonded heteroatoms such as sulfur, oxygen and nitrogen. Organic bonded heteroatoms negatively affect the catalyst in some cases.

Lower crude oils have a relatively high content of metal impurities, such as nickel, vanadium, and / or iron, for example. During processing of such crude oil, metal impurities and / or compounds of metal impurities may be deposited on the surface of the catalyst or within the void volume of the catalyst. This deposition can degrade the catalytic activity.

During the processing of lower crude oil, coke may rapidly form and / or deposit on the catalyst surface. There is a significant cost to regenerate the catalytic activity of the coke-contaminated catalyst. In addition, the high temperatures used during regeneration can lead to a decrease in catalyst activity and / or deterioration of the catalyst.

Lower crude oil may include metals (eg, calcium, potassium and / or sodium) in organic acid metal salts. Usually, conventional treatments such as desalting and / or acid washing do not separate the metals in the organic acid metal salts from the lower crude oil.

When the metals in the organic acid metal salt are present, the treatments in the conventional treatments collide with each other in many cases. Nickel and vanadium are usually deposited near the outer surface of the catalyst, but the metals in the organic acid metal salts preferentially deposit in the volume of the pores between the catalyst particles, in particular on top of the catalyst bed. On top of the catalyst bed, deposits of contaminants, for example metals in organic acid metal salts, usually cause an increase in pressure drop on the bed, causing the catalyst bed to actually occlude. In addition, the metals in the organic acid metal salts lead to rapid deactivation of the catalyst.

Lower crude oil may include organic oxygen compounds. Treatment plants that process lower crude oil with an oxygen content of at least 0.002 grams per gram of lower crude oil may encounter difficulties during processing. When the organic oxygen compounds are heated during the treatment process, they are difficult to remove from the treated crude oil and / or corrode / contaminate the equipment during the treatment process, resulting in higher order oxidizing compounds (eg ketones and And / or acids formed by oxidation of alcohols and / or acids formed by oxidation of ethers).

Lower crude oil may include hydrogen deficient hydrocarbons. In the case of treating hydrogen deficient hydrocarbons, especially when an unsaturated amount obtained from the cracking process is produced, usually a constant amount of hydrogen must be added. Hydrogenation during treatment, usually involving the use of an active hydrogenation catalyst, is necessary to prevent the unsaturated portion from forming coke. Hydrogen is costly to transport to its manufacturing and / or processing facilities.

Lower crude oil shows instability during processing at conventional facilities. Crude oil instability leads to phase separation of components during processing and / or formation of undesirable byproducts (eg, hydrogen sulfide, water, carbon dioxide).

Conventional processing processes often lack the ability to change selected properties in the lower crude oil without significantly altering other characteristics in the lower crude oil. For example, conventional processing processes lack the ability to significantly lower TAN in lower crude oil while only changing the content of certain components (such as sulfur or metallic impurities) in the lower crude oil as desired.

Some treatments to improve the quality of crude oil include the addition of diluents to lower crude oil to lower the weight percentage of ingredients contributing to undesirable properties. However, adding a diluent generally increases the cost of processing the lower crude oil due to the cost of entering the diluent and / or the increasing cost of handling the lower crude oil. The addition of diluents to lower crude oil may, in some cases, reduce the stability of the crude oil.

U.S. Patent No. 6,547,957 to Sudhhakar et al., U.S. Patent No. 6,277,269 to Meyers et al., U.S. Patent No. 6,063,266 to Grande et al., Bearden U.S. Patent 5,928,502 to U.S. Pat., U.S. Patent 5,914,030 to Vierden et al., U.S. Patent 5,897,769 to Trachte et al., U.S. Patent 5,871,636 to Trazette et al. U. S. Patent No. 5,851, 381 to Tanaka et al. Describes various processing processes, systems and catalysts for processing crude oil. The treatments, systems and catalysts described in these patent documents are limited in their application due to the many technical problems presented above.

In short, lower crude oil typically has undesirable properties (eg, a relatively high TAN, a tendency to become unstable during processing, and / or a tendency to consume a relatively large amount of hydrogen during processing). Other undesirable properties include having large amounts of undesirable components (eg, residues, organic bond heteroatoms, metal impurities, metals in organic acid metal salts and / or organic oxygen compounds). These characteristics cause problems such as increased corrosion, shorter catalyst life, process plugging, and / or increased hydrogen consumption during conventional transfer and / or treatment facilities. Therefore, there is a significant economic and technical need for improved systems, methods and / or catalysts for converting lower crude oil into crude oil products having more desirable properties. There is also a significant economic and technical need for improved systems, methods and / or catalysts that can change selected properties of the lower crude oil while selectively varying other characteristics of the lower crude oil.

Typically, the inventions described herein relate to systems, methods, and catalysts for converting a crude oil feed into a crude product and, in some embodiments, a final product comprising a non-condensable gas. In addition, the inventions described herein relate to compositions having new combinations of the components. Such compositions can be obtained using the systems and methods described herein.

The present invention provides a contacting step of contacting a crude oil feed with at least one catalyst to produce a final product comprising the crude oil product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and the crude feed Has a TAN of at least 0.3, and at least one of the catalysts has a pore size distribution with an average pore diameter in the range of 90 kPa to 180 kPa, with at least 60% of the total number of porosities in the pore size distribution A pore diameter of less than 45 mm pore diameter, wherein the pore size distribution is controlled by the contacting step obtained by ASTM specification D4282, and controlling contact conditions such that the crude product has a TAN of up to 90% of the TAN of the crude feed. As a step, here TAN provides a process for preparing a crude oil product comprising said control step as obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil The feed has a TAN of at least 0.3 and at least one of the catalysts has a pore size distribution having an average pore diameter of at least 90 mm as determined by ASTM specification D4282, wherein the catalyst having a pore size distribution is a catalyst. The contacting step having 0.0001 grams to 0.08 grams when calculating molybdenum, one or more molybdenum compounds, or mixtures thereof per gram as the weight of molybdenum, and the crude product having a TAN of at most 90% of the TAN of the crude feed. A control step for controlling contact conditions, wherein TAN includes the control step obtained by ASTM specification D664. It provides a process for the production of crude product.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and ASTM specifications. The crude oil feed has a TAN of at least 0.3, as determined by D664, and at least one of the catalysts, as determined by ASTM specification D4282, has a pore size distribution having an average pore diameter of at least 180 mm 3, and the pore size The catalyst having a distribution comprises the contacting step comprising one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product is supplied to the crude oil feed A control step of controlling the contact conditions to have a TAN of up to 90% of the TAN of the water, where TAN is ASTM specification D66 It provides a process for producing a crude oil product comprising the control step obtained by 4.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and ASTM specifications. Obtained from D664, the crude oil feed has a TAN of at least 0.3, and at least one of the catalysts comprises: (a) one or more metals from Group 6 on the periodic table, one or more metals from Group 6 on the periodic table; One or more compounds, or mixtures thereof, and (b) one or more metals from Group 10 on the periodic table, one or more compounds of one or more metals from Group 10 on the periodic table, or mixtures thereof, Wherein the molar ratio of the total Group 10 metal to the total Group 6 metal is in the range of 1-10, and the crude product is the TAN of the crude feed A control step of controlling the contact condition to have a TAN of up to 90%, wherein TAN is provided a method for preparing oil product comprising a step of obtaining the control by the ASTM D664 standard.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil The feed has a TAN of at least 0.3, wherein the one or more catalysts are (a) one or more metals from Group 6 on the periodic table, 0.0001 to 0.06 grams, calculated as the weight of metal per gram of the first catalyst, 6 on the periodic table. One or more compounds of one or more compounds of one or more metals from the group, or (b) one or more from Group 6 on the periodic table of at least 0.02 grams, calculated as the weight of the metal per gram of the second catalyst Said contact comprising a second catalyst having metals, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof And controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed, wherein the TAN comprises the control step obtained by ASTM specification D664. To provide.

In addition, the present invention provides a process for preparing a mixture of (a) one or more metals from Group 5 on the periodic table, one or more compounds of one or more metals from Group 5 on the periodic table, or mixtures thereof, (b) by x-ray diffraction And a carrier material having a theta alumina content of at least 0.1 grams per gram of carrier material, wherein the catalyst provides a catalyst composition having a pore size distribution having an average pore diameter of at least 230 kPa as determined by ASTM specification D4282.

In addition, the present invention provides a process for preparing a mixture of (a) one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, (b) by x-ray diffraction And a carrier material having a theta alumina content of at least 0.1 grams per gram of carrier material, wherein the catalyst provides a catalyst composition having a pore size distribution having an average pore diameter of at least 230 kPa as determined by ASTM specification D4282.

In addition, the present invention relates to (a) one or more metals from Group 5 on the periodic table, one or more compounds of one or more metals from Group 5 on the periodic table, one or more metals from Group 6 on the periodic table, Group 6 on the periodic table One or more compounds of one or more metals or mixtures thereof, (b) a carrier material having a content of at least 0.1 gram of theta alumina per gram of carrier material, as determined by x-ray diffraction, the catalyst being ASTM Provided is a catalyst composition having a pore size distribution having an average pore diameter of at least 230 mm 3 when determined according to specification D4282.

The present invention also provides a compounding step of combining a carrier with one or more metals to form a carrier / metal mixture, wherein the carrier comprises theta alumina, wherein the one or more metals are from one or more metals from Group 5 on the periodic table. For example, the compounding step comprising one or more compounds of one or more metals from Group 5 on the periodic table, or mixtures thereof, and heat to form the catalyst by heating the theta alumina carrier / metal mixture at a temperature of at least 400 ° C. As a treatment step, wherein the catalyst provides a method for preparing a catalyst comprising the step having a pore size distribution having an average pore diameter of at least 230 mm 3 as determined by ASTM specification D4282.

The present invention also provides a compounding step of combining a carrier with one or more metals to form a carrier / metal mixture, wherein the carrier comprises theta alumina, wherein the one or more metals are from one or more metals from Group 6 on the periodic table. For example, the compounding step comprising one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and heat to form the catalyst by heating the theta alumina carrier / metal mixture at a temperature of at least 400 ° C. As a treatment step, wherein the catalyst provides a method for producing a catalyst comprising the heat treatment step having a pore size distribution having an average pore diameter of at least 230 mm 3 as determined by ASTM specification D4282.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil The feed has a TAN of at least 0.3, at least one of the catalysts has a pore size distribution having an average pore diameter of at least 180 mm as determined by ASTM specification D4282, and the catalyst having the pore size distribution is theta Said contacting step comprising alumina and at least one metal from Group 6 on the periodic table, at least one compound of at least one metal from Group 6 on the periodic table, or mixtures thereof, and wherein the crude product is obtained from the TAN of the crude feed A control step that controls contact conditions to have a TAN of up to 90%, where TAN is in accordance with ASTM specification D664. Obtain provides a method for producing oil products including the control step.

The present invention also provides a contacting step of contacting a crude oil feed with at least one catalyst in the presence of a hydrogen source to produce a final product comprising the crude oil product, the crude oil product having a liquid mixture at 25 ° C., 0.101 MPa. Present, the crude feed has a TAN of at least 0.3, the crude feed has an oxygen content of at least 0.0001 grams per gram of crude oil feed, and at least one of the catalysts as determined by ASTM specification D4282 The contacting step having a pore size distribution having an average pore diameter of at least 90 kPa, and in order to reduce the TAN, the crude product has a TAN of up to 90% of the TAN of the crude feed and the content of organic oxygen-containing compounds Contact conditions so that the crude oil product has an oxygen content of up to 90% of the oxygen content of the crude feed. As a control step of controlling the TAN, where TAN is obtained by ASTM standard D664, the oxygen content is provided by the ASTM standard E385 provides a method for producing a crude oil product comprising the control step.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil The feed has a TAN of at least 0.1 and at least one of the catalysts is at least one metal from Group 6 on the periodic table, at least 0.001 gram per gram of catalyst, calculated from the weight of metal Said contacting step having one or more compounds of metals, or mixtures thereof, and a liquid space velocity in the contacting region of at least 10 h ⁻¹ , wherein the crude product has a TAN of at most 90% of the TAN of the crude feed. A control step of controlling the contact conditions to have, wherein the TAN is of a crude oil product comprising said control step obtained by ASTM specification D664 It provides a manufacturing method.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst in the presence of a hydrogen source to produce a final product comprising the crude product, wherein the crude product is brought to a liquid mixture at 25 ° C., 0.101 MPa. Wherein the crude feed has a TAN of at least 0.1, the crude feed has a sulfur content of at least 0.0001 grams per gram of crude oil feed, and at least one of the catalysts is from Group 6 on the periodic table. The contacting step comprising at least one metal, at least one compound of at least one metal from group 6 on the periodic table, or a mixture thereof, and the crude oil feed during contacting is selected to prevent phase separation of the crude oil feed during contacting. Consume molecular hydrogen in proportion, and the liquid space velocity at one or more contacting zones is at least 10 h ⁻¹ , and the crude product A control step of controlling the contact conditions to have a TAN of up to 90% of the TAN of the crude feed, wherein the crude product has a sulfur content of 70-130% of the sulfur content of the crude feed, wherein TAN is ASTM specification D664 And the sulfur content is determined by ASTM specification D4294.

The invention also provides a contacting step of contacting a crude oil feed with one or more catalysts in the presence of a gaseous hydrogen source to produce a final product comprising the crude oil product present in a liquid mixture at 25 ° C., 0.101 MPa, and The crude oil feed during contacting provides a control step of controlling the contacting conditions to consume hydrogen at a selected rate to prevent phase separation of the crude oil feed during contacting.

The invention also provides a contacting step of contacting a crude feed with hydrogen in the presence of one or more catalysts to produce a final product comprising the crude product present in a liquid mixture at 25 ° C., 0.101 MPa, and said crude feed Contacting hydrogen at this first hydrogen consumption condition and then contacting hydrogen at the second hydrogen consumption condition, the first hydrogen consumption condition is different from the second hydrogen consumption condition, and the net hydrogen consumption at the first hydrogen consumption condition is crude oil. Controlled to prevent the P-value of the feed / final product mixture from decreasing below 1.5, wherein one or more properties of the crude product are controlled to be changed by up to 90% with respect to each one or more properties of the crude feed It provides a process for producing a crude oil product comprising a control step.

The invention also provides a contacting step of contacting a crude feed with one or more catalysts at a first temperature followed by contact at a second temperature to produce a final product comprising the crude product. A crude oil feed at 25 ° C., 0.101 MPa, wherein the crude feed has at least 30 ° C. lower than the second contact temperature, the contacting step having a TAN of at least 0.3, and the crude product With a TAN of up to 90% in relation to the TAN of the crude oil feed, the TAN provides a process for producing a crude oil product comprising a control step obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.3, the crude feed has a sulfur content of at least 0.0001 grams per gram of crude oil feed, and at least one of the catalysts comprises one or more metals from Group 6 on the periodic table, The contacting step comprising one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product has a TAN of up to 90% of the TAN of the crude feed, wherein the crude product is A control step of controlling the contact conditions to have a sulfur content of 70-130% of the sulfur content of the crude feed, wherein TAN is in accordance with ASTM specification D664. It obtained and the sulfur content provides a method for producing oil products including the control step as determined by ASTM standard D4294.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.1, the crude feed has a residual content of at least 0.1 grams per gram of the crude feed, and at least one of the catalysts is at least one metal from Group 6 on the periodic table. For example, the contacting step comprising one or more compounds of one or more metals from Group 6 on the periodic table, or a mixture thereof, and the crude product has a TAN of up to 90% of the TAN of the crude feed, Is a control step of controlling the contact conditions to have a residue content of 70-130% of the residue content of the crude feed, wherein TAN Is obtained by ASTM specification D664 and the residue content is obtained by the ASTM specification D5307.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.1, the crude feed has a VGO content of at least 0.1 grams per gram of the crude feed, and at least one of the catalysts is one or more metals from Group 6 on the periodic table. The contacting step comprising one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product has a TAN of up to 90% of the TAN of the crude feed, A control step of controlling the contact conditions to have a residue content of 70-130% of the VGO content of the crude feed, wherein the VGO content is ASTM It provides a method for producing oil products including the control step as determined by the interval D5307.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.3, and at least one of the catalysts comprises one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or The contacting step, which is obtained by combining with a mixture of these to form a catalyst precursor and heating the catalyst precursor at a temperature below 500 ° C. in the presence of one or more sulfur containing compounds to form a catalyst, and the crude product is the crude oil. Crude oil production comprising a control step of controlling the contact conditions to have a TAN of up to 90% of the TAN of the feed It provides a process for the production of.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a viscosity of at least 10 cSt at 37.8 ° C. (100 ° F.), wherein the crude feed has a specific gravity of at least 10 APT, and at least one of the catalysts is in Group 6 on the periodic table. The contacting step comprising one or more metals from, one or more compounds of one or more metals from Group 6 on the periodic table, or a mixture thereof, and the crude product has a maximum of 90 viscosity of the crude feed at 37.8 ° C. Having a viscosity at 37.8 ° C. of percent, the crude product controls the contact conditions to have an API specific gravity of 70-130% of the API specific gravity of the crude feed. A control step, in which the API gravity is determined by ASTM standard D6822, viscosity provides a method for producing oil products including the control step as determined by ASTM standard D2669.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.1 and the at least one catalyst comprises at least one catalyst and additional catalyst comprising vanadium, at least one compound of vanadium, or mixtures thereof, the further catalyst comprising at least one 6 The contacting step comprising group metals, one or more compounds of one or more Group 6 metals, or mixtures thereof, and control to control the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed. As a step, here TAN provides a process for producing a crude product comprising said control step as obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The contacting step having a feed having a TAN of at least 0.1, generating hydrogen during the contacting, and controlling the contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed. Wherein TAN provides a process for the production of crude oil products comprising said control step as obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.1, wherein at least one of the catalysts comprises at least one of vanadium, at least one compound of vanadium, or a mixture thereof, and a contact temperature of at least 200 ° C. and the crude product A control step of controlling the contact conditions to have a TAN of at most 90% of the TAN of the crude feed, wherein the TAN provides a method of making a crude product comprising the control step as obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.1, wherein at least one of the catalysts comprises the contacting step comprising vanadium, one or more compounds of vanadium, or mixtures thereof, supplying a gas comprising a hydrogen source during contacting. Wherein the gas flow is provided in a direction opposite to the flow of the crude feed, and the control step of controlling contact conditions such that the crude product has a TAN of at most 90% of the TAN of the crude feed. TAN provides a process for the production of crude oil products comprising the control step obtained by ASTM specification D664.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, at least one of the catalysts comprising vanadium, one or more compounds of vanadium, or mixtures thereof, the vanadium catalyst The contacting step having a pore size distribution having an average pore diameter of at least 180 mm 3, and the crude product is subjected to contact conditions such that the total Ni / V / Fe content is at most 90% of the Ni / V / Fe content of the crude feed. As a controlling step for controlling, wherein the Ni / V / Fe content provides a process for producing a crude oil product comprising said controlling step as obtained by ASTM standard D5708.

The invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the catalyst At least one of these catalysts includes vanadium, one or more compounds of vanadium, or mixtures thereof, wherein the crude oil feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof Wherein said crude feed has a total content of alkali metal and alkaline earth metal in a metal salt of organic acid of at least 0.00001 gram per gram of crude oil feed, and said crude product is contained in the metal salt of organic acid of said crude feed In metal salts of organic acids up to 90% of the content of alkali metals and alkaline earth metals A control step of controlling the contact conditions to have a total content of kali metal and alkaline earth metal, wherein the content of alkali metal and alkaline earth metal in the metal salt of the organic acid comprises said control step as determined by ASTM standard D1318. It provides a method for producing.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals, at least one of the catalysts having a pore size distribution having an average pore diameter in the range of 90 kPa to 180 kPa, wherein at least 60% of the total number of porosities of the pore size distribution is the average pore Having a pore diameter within 45 mm of the diameter, wherein the pore size distribution is determined by ASTM specification D4282. The contacting step, and the crude product controls the contact conditions to have a total content of alkali metals and alkaline earth metals in the metal salts of the organic acid up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of the organic acids of the crude feed As a control step, wherein the content of the alkali metal and alkaline earth metal in the metal salt of the organic acid provides a method for producing a crude oil product comprising the control step obtained by ASTM standard D1318.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, at least one of the catalysts having a pore size distribution having an average pore diameter in the range of 90 kPa to 180 kPa, At least 60% of the total pore size distribution has a pore diameter within 45 mm of the average pore diameter, wherein the pore size distribution is determined by ASTM specification D4282, and the crude product contains Ni / A control step of controlling the contact conditions to have a total Ni / V / Fe content of up to 90% of the V / Fe content, wherein the Ni / V / Fe content is obtained by ASTM specification D5708. It provides a method for producing oil products including the control step.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present as a liquid mixture at 25 ° C., 0.101 MPa, and the crude oil feed Water has a total content of alkali metals and alkaline earth metals in at least 0.00001 grams of metal salts of organic acids per gram of crude oil feed, at least one of the catalysts having an average porosity of at least 180 mm as determined by ASTM specification D4282. Said contacting step comprising a pore size distribution having a diameter, said catalyst comprising one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and Crude oil products are characterized by the highest content of alkali and alkaline earth metals in the metal salts of organic acids of the crude feed. A control step of controlling the contact conditions to have a total content of alkali metal and alkaline earth metal in the metal salt of the organic acid of 90%, wherein the content of the alkali metal and alkaline earth metal in the metal salt of the organic acid is determined by ASTM specification D1318. It provides a process for producing a crude oil product comprising a control step.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals, at least one of the catalysts having a pore size distribution having an average pore diameter of at least 230 kPa, as determined by ASTM specification D4282, wherein the catalyst is in Group 6 on the periodic table. One or more metals derived, one or more compounds of one or more metals from Group 6 on the periodic table, Or the contacting step having a pore size distribution comprising a mixture thereof, and the crude oil product comprises alkali metals and alkalis in the metal salts of organic acids up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of organic acids of the crude feed A control step of controlling the contact conditions to have a total content of the earth metal, wherein the content of alkali metal and alkaline earth metal in the metal salt of the organic acid is determined by ASTM specification D1318. to provide.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, with at least one of the catalysts having a pore size distribution having an average pore diameter of at least 230 kPa as determined by ASTM specification D4282. Said contacting step having a pore size distribution comprising one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product is A control step of controlling the contact conditions to have a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the feed, where Ni / V / Fe The amount provides a process for producing a crude oil product comprising the control step as determined by ASTM specification D5708.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals, at least one of the catalysts having a pore size distribution having an average pore diameter of at least 90 kPa, as determined by ASTM specification D4282, wherein the catalyst has a molybdenum per gram of catalyst. 0.0001 to 0.3 grams of molybdenum, one or more molybdenum compounds, calculated as weight, or Said contacting step having a total molybdenum content of the mixture of said mixtures, and said crude oil product comprises a total of alkali metals and alkaline earth metals in the metal salt of organic acids up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of organic acids of said crude feed. A control step of controlling the contact conditions to have a content, wherein the content of alkali metals and alkaline earth metals in the metal salts of the organic acid comprises the above control step obtained by ASTM specification D1318.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a TAN of at least 0.3, the crude feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, and at least one of the catalysts was determined by ASTM specification D4282. Has a pore size distribution having an average pore diameter of at least 90 mm 3, and the catalyst has a total molybdenum content of 0.0001 grams to 0.3 grams of molybdenum, one or more molybdenum compounds, or mixtures thereof, calculated as the weight of molybdenum per gram of catalyst The contacting step, and the crude product has a TAN of at most 90% of the TAN of the crude feed, the crude product being Having a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the feed, where the Ni / V / Fe content is obtained by ASTM specification D5708, and TAN is the control obtained by ASTM specification D644 It provides a process for producing a crude oil product comprising the steps.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof, wherein the crude feed comprises at least 0.00001 grams of alkali metal in metal salts of organic acids per gram of crude oil feed And a total content of alkaline earth metals, at least one of the catalysts comprising: (a) one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or (B) one or more metals from Group 10 of the Periodic Table, one or more groups from Group 10 of the Periodic Table At least one compound of metals, or mixtures thereof, wherein the contacting step wherein the molar ratio of the total Group 10 metal to the total Group 6 metal is in the range of 1-10, and the crude product is an organic acid of the crude feed A control step of controlling the contact conditions to have a total content of alkali metal and alkaline earth metal in the metal salt of the organic acid of up to 90% of the content of the alkali metal and alkaline earth metal in the metal salt of wherein the alkali metal and alkali in the metal salt of the organic acid The content of earth metals provides a process for the production of crude oil products comprising said control step as determined by ASTM standard D1318.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, at least one of the catalysts comprising: (a) one or more metals from Group 6 on the periodic table, Group 6 on the periodic table; One or more compounds of one or more metals derived from, or mixtures thereof, (b) one or more metals from group 10 on the periodic table, one or more compounds of one or more metals from group 10 on the periodic table, or mixtures thereof Wherein the molar ratio of the total Group 10 metal to the total Group 6 metal is in the range of 1-10, and the crude product contains the Ni / V / Fe content of the crude feed. It has a total Ni / V / Fe content of at most 90%, and wherein Ni / V / Fe content is provide a method for producing oil products including the control step as determined by ASTM standard D5708.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals, wherein the one or more catalysts are (a) a first catalyst, the first catalyst having one or more metals from Group 6 on the periodic table of 0.0001 to 0.06 grams per gram of the first catalyst, Having one or more compounds of one or more metals from Group 6 on the periodic table, calculated as the weight of the metal, or mixtures thereof The first catalyst, (b) a second catalyst, wherein the second catalyst is from one or more metals from Group 6 on the periodic table of 0.02 grams calculated as the weight of metal per gram of the second catalyst, from Group 6 on the periodic table The contacting step comprising the second catalyst having one or more compounds of one or more metals, or mixtures thereof, and the crude product comprises a maximum of 90 content of alkali metal and alkaline earth metal in the metal salt of the organic acid of the crude feed A control step of controlling the contact conditions to have a total content of alkali metal and alkaline earth metal in the metal salt of the organic acid of%, wherein the content of the alkali metal and alkaline earth metal in the metal salt of the organic acid is determined by ASTM specification D1318. It provides a process for producing a crude oil product comprising the steps.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals, wherein at least one of the catalysts is at least one metal from Group 6 on the periodic table, at least 0.001 gram per gram of catalyst, calculated from the weight of the metal Said contacting step having at least one compound of at least metals, or mixtures thereof, and contacting The liquid space velocity in the region is at least 10 h ⁻¹ , and the crude oil product is composed of alkali metals and alkaline earth metals in the metal salts of the organic acids up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of the organic acids of the crude feed. A control step of controlling the contact conditions to have a total content, wherein the content of alkali metals and alkaline earth metals in the metal salts of the organic acid comprises the above control step obtained by ASTM specification D1318.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed and at least one of the catalysts is from Group 6 on the periodic table of at least 0.001 grams per gram of catalyst calculated as the weight of the metal. The contacting step with one or more metals, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the liquid space velocity in the contacting zone is at least 10 h ⁻¹ , and the crude product is Having a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude oil feed, wherein the Ni / V / Fe content comprises the control step as determined by ASTM specification D5708 It provides a process for producing a crude oil product.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has an oxygen content of at least 0.0001 grams per gram of crude oil feed, and a sulfur content of at least 0.0001 grams, wherein at least one of the catalysts is from one or more metals from Group 6 on the periodic table, Group 6 on the periodic table. Said contacting step having one or more compounds of one or more metals, or mixtures thereof, and the crude product has an oxygen content of up to 90% of the oxygen content of the crude feed, the crude product having a sulfur content of the crude feed A control step of controlling the contact conditions to have a sulfur content of 70-130% of wherein the oxygen content is ASTM specification E38 Obtained by 5, the sulfur content provides a process for the production of crude oil products comprising said control step obtained by ASTM specification D4294.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams and a sulfur content of at least 0.0001 grams per gram of crude oil feed, at least one of the catalysts being at least one metal from Group 6 on the periodic table, The contacting step with one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product comprises a total Ni / V / of up to 90% of the Ni / V / Fe content of the crude feed. Having a Fe content, the crude product is a control step of controlling the contact conditions to have a sulfur content of 70-130% of the sulfur content of the crude feed, wherein the Ni / V / Fe content is an ASTM specification. Provided by D5708, the sulfur content provides a process for the production of crude oil products comprising said control step as obtained by ASTM specification D4294.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises at least one alkali metal salt of at least one organic acid, at least one alkaline earth metal salt of at least one organic acid, or a mixture thereof, wherein the crude feed is at least 0.00001 gram of metal salt of organic acid per gram of crude oil feed And a total content of alkaline earth metals and a residue content of at least 0.1 grams, wherein at least one of the catalysts is one or more metals from Group 6 on the periodic table, one or more metals from Group 6 on the periodic table The contacting step with the compounds, or mixtures thereof, and the crude product is the crude oil Having a total content of alkali metals and alkaline earth metals in the metal salts of organic acids of up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of the organic acids of the feed, wherein the crude oil product is 70-130 of the residue content of the crude feed A control step of controlling the contact conditions to have a residue content of%, wherein the alkali metal and alkaline earth metal content in the metal salt of the organic acid is obtained by ASTM specification D1318, and the residue content is obtained by ASTM specification D5307. It provides a process for producing a crude oil product comprising the control step.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a residual content of at least 0.1 grams per gram of crude oil feed and a total Ni / V / Fe content of at least 0.00002 grams, wherein at least one of the catalysts comprises at least one metal from Group 6 on the periodic table, Said step having one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof, and the crude product comprises up to 90% of the total Ni / V / Fe content of the Ni / V / Fe content of the crude feed Content, the crude product is a control step of controlling the contact conditions to have a residue content of 70-130% of the residue content of the crude feed, wherein the Ni / V / Fe content is AS It provides a process for the production of crude oil products comprising the above control steps as obtained by TM specification D5708 and the residue content as obtained by ASTM specification D5307.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof, wherein the crude feed comprises at least 0.1 grams of vacuum gas oil per gram of crude oil feed (“VGO ") Content and the total content of alkali metals and alkaline earth metals in a metal salt of 0.0001 grams of organic acid, at least one of said catalysts being at least one metal from Group 6 on the periodic table, a work from Group 6 on the periodic table The contacting step with one or more compounds of the above metals, or mixtures thereof, and the crude product Having a total content of alkali metals and alkaline earth metals in the metal salts of the organic acids up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of the organic acids of the crude oil feed, wherein the crude product contains 70-130 of the VGO content of the crude feed A control step of controlling the contact conditions to have a VGO content of%, wherein the VGO content is obtained by ASTM specification D5307, and the content of alkali metal and alkaline earth metal in the metal salt of organic acid is obtained by ASTM specification D1318. It provides a process for producing a crude oil product comprising the steps.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams and a VGO content of at least 0.1 grams per gram of crude oil feed, with at least one of the catalysts having at least one metal from Group 6 on the periodic table, periodic table The contacting step with one or more compounds of one or more metals from Group 6 of the bed, or mixtures thereof, and the crude product contains up to 90% of the total Ni / V / Fe of the Ni / V / Fe content of the crude feed Content, the crude product is a control step of controlling the contact conditions to have a VGO content of 70-130% of the VGO content of the crude feed, wherein the VGO content is ASTM specification D5307. And a Ni / V / Fe content provided by the ASTM specification D5708 provides a process for the production of crude oil products comprising said control step.

The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed includes one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof, wherein the crude feed comprises at least 0.00001 grams of alkali metal in metal salts of organic acids per gram of crude oil feed And a total content of alkaline earth metals, wherein at least one of the catalysts comprises one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or To form a catalyst precursor and combine the catalyst precursor with one or more sulfur containing compounds The contacting step obtainable by forming the catalyst by heating at a temperature of less than 400 ° C. in the presence of them, and the crude oil product comprises up to 90% of the content of alkali metals and alkaline earth metals in the metal salts of organic acids in the crude feed. A control step of controlling the contact conditions to have a total content of an alkali metal and an alkaline earth metal in the metal salt of the organic acid, wherein the content of the alkali metal and the alkaline earth metal in the metal salt of the organic acid comprises the control step obtained by ASTM specification D1318 It provides a process for producing a crude oil product.

 The present invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is present in a liquid mixture at 25 ° C., 0.101 MPa, the crude oil The feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude oil feed, at least one of the catalysts comprising at least one metal from Group 6 on the periodic table, Group 6 on the periodic table The above obtainable by combining with one or more compounds of one or more metals, or mixtures thereof, to form a catalyst precursor and heating the catalyst precursor at a temperature below 400 ° C. in the presence of one or more sulfur containing compounds to form the catalyst. Contacting step, and contacting conditions such that the crude product has a total Ni / V / Fe content of up to 90% of the Ni / V / Fe content of the crude feed. A control step of controlling, and wherein Ni / V / Fe content is provide a method for producing oil products including the step of obtaining control by ASTM specification D5708.

 The present invention also provides a minimum 0.001 gram of hydrocarbon having a boiling range distribution of 95 ° C. to 260 ° C. at 0.101 MPa per gram of crude oil composition, and a minimum 0.001 gram of hydrocarbon having a boiling range distribution of 260 ° C. to 320 ° C. at 0.101 MPa. A crude oil composition having a hydrocarbon having a boiling range distribution from 320 ° C. to 650 ° C. at MPa of at least 0.001 grams and more than 0 grams per gram of crude oil product but less than 0.01 grams of one or more catalysts.

In addition, the present invention provides a weight ratio of MCR content to at least 0.01 grams of sulfur as determined by ASTM specification D4294 per gram of composition, at least 0.2 grams of residue as determined by ASTM specification D5307, and to a C ₅ asphaltene content of at least 1.5. Wherein the MCR content is determined by ASTM specification D4530 and the C ₅ asphaltene content provides a crude oil composition obtained by ASTM specification D2007.

The invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is condensable at 25 ° C., 0.101 MPa, and the crude oil feed Water has an MCR content of at least 0.001 grams per gram of crude oil feed, at least one of the catalysts comprising at least one metal from Group 6 on the periodic table, one or more metals from Group 6 on the periodic table The contacting step obtainable by combining the above compounds, or mixtures thereof, to form a catalyst precursor and heating the catalyst precursor at a temperature below 500 ° C. in the presence of one or more sulfur containing compounds to form a catalyst, and the crude oil The product is a control step of controlling the contact conditions to have an MCR content of up to 90% of the MCR content of the crude oil feed. Here, the MCR content provides a process for the production of crude oil products comprising said control step as obtained by ASTM specification D4530.

The invention also provides a contacting step of contacting a crude feed with at least one catalyst to produce a final product comprising the crude product, wherein the crude product is condensable at 25 ° C., 0.101 MPa, and the crude oil feed Water has an MCR content of at least 0.001 grams per gram of crude oil feed, at least one of the catalysts having a pore size distribution having an average pore diameter in the range of 70 kPa to 180 kPa, and of the total number of pores in the pore size distribution. At least 60% has a pore diameter within 45 mm of the average pore diameter, wherein the pore size distribution is such that the contacting step obtained by ASTM specification D4282, and that the crude product has an MCR of up to 90% of the MCR of the crude feed A control step for controlling the contact conditions, wherein MCR is a crude oil product comprising the control step obtained by ASTM specification D4530. To provide a crude method.

In addition, the present invention has at least 0.004 grams of oxygen as determined by ASTM specification E385 per gram of composition, at least 0.003 grams of sulfur as determined by ASTM specification D4294 and at least 0.3 grams residue as determined by ASTM specification D5307. It provides a crude oil composition.

The present invention also provides a maximum of 0.004 grams of oxygen per gram of composition as determined by ASTM standard E385, up to 0.003 grams of sulfur as determined by ASTM standard D4294, up to 0.04 grams of basic nitrogen as determined by ASTM standard D2896, ASTM A crude oil composition having a residue of at least 0.2 grams as determined by specification D5307 and having a TAN of at most 0.5 as determined by ASTM specification D664.

In addition, the present invention has a minimum of 0.001 grams of sulfur per gram of composition and at least 0.2 grams of residue as determined by ASTM standard D5307 per gram of composition, the composition having a C ₅ asphaltene content of at least 1.5. Having a weight ratio of MCR to the composition, the composition having a TAN up to 0.5, wherein TAN is obtained by ASTM specification D664, the weight of MCR is obtained by ASTM specification D4530, and the weight of C ₅ asphaltenes is determined by ASTM specification D2007. It provides a crude oil composition obtained by.

The present invention, in some embodiments, also provides a crude oil feed in combination with one or more methods or compositions according to the invention, which crude oil feed has not been processed in (a) a refining plant, Distilled and / or fractionally distilled and (b) having components having a carbon number of more than 4 and the crude feed also has at least 0.5 grams of these components per gram of crude oil feed and (c) a portion of which is between 0.101 MPa and 100 Boiling range distribution below ° C, Boiling range distribution from 0.101 MPa to 100 ° C to 200 ° C, Boiling range distribution from 0.101 MPa to 200 ° C to 300 ° C, Boiling range distribution from 0.101 MPa to 300 ° C to 400 ° C, and Hydrocarbons having a boiling range distribution from 0.101 MPa to 400 ° C.-650 ° C. and (d) hydrocarbon water having a boiling range distribution below 100 ° C. at least 0.001 gram of 0.101 MPa per gram crude oil feed. , Hydrocarbons having a boiling range distribution in the range 100 ° C. to 200 ° C. at least 0.001 grams of 0.101 MPa, hydrocarbons having a boiling range distribution in the range 200 ° C. to 300 ° C. at least 0.001 grams of 0.101 MPa, at least 0.001 grams of 0.101 MPa Hydrocarbons having a boiling range distribution in the range 300 ° C. to 400 ° C., and hydrocarbons having a boiling range distribution in the range 400 ° C. to 650 ° C. at least 0.001 grams of 0.101 MPa, and (e) at least 0.1, at least 0.3, or 0.3 to 20 (T) has an initial boiling point of at least 200 ° C. at 0.101 MPa, (g) contains nickel, vanadium and iron, and (h) at least 0.00002 per gram of crude oil feed. Grams total Ni / V / Fe, (i) contain sulfur, (j) at least 0.0001 grams or 0.05 grams of sulfur per gram of crude oil feed, and (k) at least 0.001 grams VGO per gram of crude oil feed, (l) per gram of crude oil feed (N) one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof (o) Organic acid zinc salts, and / or (p) at least one organic acid arsenic salt.

The present invention, in some embodiments, also provides a crude oil feed obtainable by combining naphtha and compounds more volatile than naphtha from crude oil in combination with one or more methods or compositions according to the present invention.

The present invention, in certain embodiments, comprises a method of contacting a crude oil feed with one or more catalysts to produce a final product comprising a crude oil product in combination with one or more methods or compositions according to the present invention. Also provided, in which the crude oil feed and the crude oil product are both C ₅ Has asphaltene content and MCR content, and (a) crude oil feed C ₅ The contact conditions are controlled such that the sum of asphaltene content and crude feed MCR content is S, the crude product C ₅ asphaltene content and crude product MCR content is S ', and S' is up to 99% of S; and And / or (b) the contact conditions are controlled such that the weight ratio of the MCR content of the crude product to the C ₅ asphaltene content of the crude product is in the range 1.2 to 2.0, or 1.3 to 1.9.

The invention, in some embodiments, in combination with one or more methods or compositions according to the invention, comprises: (a) gas phase, (b) hydrogen gas, (c) methane, (d) light hydrocarbon ), (e) an inert gas, and / or (f) mixtures thereof as a hydrogen source.

The present invention, in certain embodiments, comprises a method of contacting a crude oil feed with one or more catalysts to produce a final product comprising a crude oil product in combination with one or more methods or compositions according to the present invention. It is also provided, in which the crude oil feed is contacted at an offshore facility or in a contact area connected to the offshore facility.

The present invention, in some embodiments, in contact with one or more methods or compositions according to the invention, contacting a crude oil feed with one or more catalysts in the presence of a gas and / or hydrogen source, and (a) The proportion of gaseous hydrogen source to crude oil feed ranges from 5 to 800 normal cubic meters of gaseous hydrogen source per cubic meter of crude oil feed in contact with at least one of the catalysts, and (b) pure hydrogen The selected rate of consumption is controlled by varying the partial pressure of its hydrogen source, and (c) the hydrogen consumption rate is less than 0.3 when the crude product has a TAN, but this hydrogen consumption is between the crude feed and the final product during contacting. Is less than the hydrogen consumption resulting in substantial phase separation, and (d) the selected hydrogen consumption rate is between 1-30 or 1-80 normal three of the hydrogen source per cubic meter of crude oil feed. In the range of product m, (e) gas and / or liquid space velocity of the hydrogen source is at least 11 h ^-1, at least 15 h ^-1, or up to 20 h ^- a ^1, (f) the gas and / or hydrogen The partial pressure of the source is controlled during contact, (g) the contact temperature is in the range of 50 to 500 ° C., and the total liquid space velocity of the gas and / or hydrogen source is in the range of 0.1 to 30 h −1, wherein the gas and And / or the total pressure of the hydrogen source is in the range of 1.0 to 20 MPa, (h) the flow of gas and / or hydrogen source is in a direction opposite to the flow of the crude oil feed, and (i) the crude product is fed to the crude oil feed H / C of 70-130% of H / C of water, (j) hydrogen consumption by crude oil feed is up to 80 and / or normal cubic meters of hydrogen per cubic meter of 1-80 or 1-50 crude oil feed (k) the crude product may be up to 90%, up to 50%, or up to the Ni / V / Fe content of the crude feed; Having a total Ni / V / Fe content of up to 10%, (l) the crude product has a sulfur content of 70-130% or 80-120% of the sulfur content of the crude feed, and (m) the crude product Having a VGO content of 70-130% or 90-110% of the VGO content of the crude oil feed, and (n) the crude product has a residue content of 70-130% or 90-110% of the residue content of the crude feed (O) the crude oil product has an oxygen content of at most 90%, at most 70%, at most 50%, at most 40%, or at most 10% of the oxygen content of the crude feed. Having a total content of alkali metals and alkaline earth metals in the metal salts of the organic acids of up to 90%, up to 50%, or up to 10% of the content of alkali metals and alkaline earth metals in the metal salts of organic acids in the crude oil feed, (q ) The P-value of the crude oil feed during contact is at least 1.5, and (r) at 37.8 ° C. The crude oil product has a viscosity of at most 90%, at most 50%, or at most 10% of the viscosity of the crude feed at 37.8 ° C., and (s) the crude oil product has an API specific gravity of 70-130% of the API gravity of the crude feed. And / or, (t) the crude oil product has a TAN of up to 90%, up to 50%, up to 30%, up to 20%, or up to 10% of the TAN of the crude oil feed and / or from 0.001 to It provides a method comprising a control step of controlling the contact conditions to have a TAN in the range of 0.5, 0.01 ~ 0.2, or 0.05 ~ 0.1.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to contact a crude feed with one or more catalysts and to reduce the content of organic oxygen-containing compounds (a) The content of selected organic oxygen compounds is reduced such that the crude product has an oxygen content of up to 90% of the oxygen content of the crude feed, and (b) at least one compound of the organic oxygen containing compounds comprises a metal salt of carboxylic acid (C) at least one of the organic oxygen-containing compounds comprises an alkali metal salt of carboxylic acid, (d) at least one of the organic oxygen-containing compounds comprises an alkaline earth metal salt of carboxylic acid, ( e) at least one of said organic oxygen-containing compounds comprises a metal salt of carboxylic acid, Wherein the metal comprises one or more metals from Group 12 of the periodic table, and (f) the crude oil product comprises up to 90% of the content of non-carboxy containing organic compounds in the crude feed And / or (g) controlling the contact conditions such that at least one of the oxygen containing compounds in the crude oil feed is derived from naphthenic acid or non-carboxyl group containing organic oxygen compounds. It also provides a method.

The present invention, in some embodiments, comprises combining one or more methods or compositions according to the present invention to contact a crude feed with at least one catalyst, wherein (a) the crude feed is At least one of the catalysts is contacted at a first temperature and then at a second temperature, wherein the contact conditions are controlled such that the first contact temperature is at least 30 ° C. lower than the second contact temperature, and (b) the The crude oil feed is contacted with hydrogen at a first hydrogen consumption condition and then with hydrogen at a second hydrogen consumption condition, the temperature of the first consumption condition being at least 30 ° C. lower than the temperature of the second consumption condition, ( c) the crude oil feed is in contact with at least one of the catalysts at a first temperature and then at a second temperature and the first contact temperature is at most 200 ° C. below the second contact temperature, (d) hydrogen gas is produced during contacting, (e) hydrogen gas is generated during contacting, and contact conditions are also controlled such that the crude oil feed consumes at least a portion of the generated hydrogen, and (f) the crude oil supply Water is contacted with the first and second catalysts and the crude feed and the first catalyst are contacted to form an initial crude product, wherein the initial crude product has a TAN of at most 90% of the TAN of the crude feed. Contacting the initial crude product and the second catalyst to form a crude product, wherein the crude product has a TAN of at most 90% of the TAN of the initial crude product, (g) contacting is performed in a bed bed reactor, (h) contacting is performed in a boiling bed reactor, (i) the crude oil feed is contacted with an additional catalyst after contacting the one or more catalysts, and (j) one or more of the catalysts Catalyst and the crude feed is contacted with an additional catalyst in the presence of a hydrogen source after contacting this vanadium catalyst, and (k) hydrogen is produced at a rate within the range of 1-20 normal cubic meters per cubic meter of crude oil feed, (l) hydrogen is produced during the contacting, the crude oil feed is contacted with a further catalyst in the presence of gas and at least a portion of the produced hydrogen, and the flow of gas also causes the flow of crude oil feed and Contact conditions are controlled to be in the opposite direction to the flow, (m) the crude oil feed is contacted with a vanadium catalyst at a first temperature and then with additional catalyst at a second temperature, the first temperature being greater than the second temperature. Contact conditions are controlled to be at least 30 ° C. low, (n) hydrogen gas is produced during the contact, the crude oil feed is contacted with additional catalyst and the additional catalyst Contact conditions are controlled to consume at least a portion of the generated hydrogen, and / or (o) the crude oil feed is subsequently contacted with a further catalyst at a second temperature and the second temperature is at least 180 ° C. How they are controlled.

 The present invention, in some embodiments, comprises combining one or more methods or compositions according to the present invention to contact a crude oil feed with one or more catalysts, wherein (a) the catalyst is a supported catalyst The carrier comprises alumina, silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof, (b) the catalyst is a supported catalyst and the carrier is porous, and (c) the method prior to sulfidation Further comprising a further catalyst heat treated at a temperature above 400 ° C., (d) at least one of the catalysts has a lifetime of at least 0.5 years, and / or (e) at least one of the catalysts Also provides a method of being in a fixed bed or in a slurry state in a crude oil feed.

The present invention, in some embodiments, comprises combining one or more methods or compositions according to the present invention to contact a crude oil feed with one or more catalysts, wherein at least one of the catalysts is A supported catalyst or bulk metal catalyst, wherein the supported catalyst or bulk metal catalyst comprises: (a) one or more metals from Groups 5-10 on the periodic table, one or more compounds of one or more metals from Groups 5-10 on the periodic table, Or mixtures thereof, and (b) one or more metals from groups 5 to 10 on the periodic table, from groups 5 to 10 on the periodic table, at least 0.0001 gram, 0.0001 to 0.6 grams, or 0.001 to 0.3 grams per gram of catalyst With one or more compounds of one or more metals, or mixtures thereof, (c) one or more metals from groups 6 to 10 of the periodic table, from groups 6 to 10 of the periodic table One or more compounds of the above metals, or mixtures thereof, (d) one or more metals from groups 7 to 10 of the periodic table, one or more compounds of one or more metals from groups 7 to 10 of the periodic table, or One or more metals from Groups 7 to 10 of the Periodic Table, one or more metals from Groups 7 to 10 of the Periodic Table, including mixtures thereof, and (e) 0.0001 to 0.6 grams or 0.001 to 0.3 grams of catalyst per gram Compounds, or mixtures thereof, comprising (f) one or more metals from Groups 5-6 on the periodic table, one or more compounds of one or more metals from Groups 5-6 on the periodic table, or mixtures thereof (g) one or more metals from Group 5 on the periodic table, one or more compounds of one or more metals from Group 5 on the periodic table, or mixtures thereof; Sugar, at least 0.0001 grams, 0.0001 to 0.6 grams, 0.001 to 0.3 grams, 0.005 to 0.1 grams, or 0.01 to 0.08 grams of one or more metals from Group 5 on the periodic table, one or more of one or more metals from Group 5 on the periodic table Compounds, or mixtures thereof, comprising (i) one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof (j) 0.0001 to 0.6 grams, 0.001 to 0.3 grams, 0.005 to 0.1 grams, 0.01 to 0.08 grams of one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or (K) one or more metals from Group 10 on the periodic table, one or more compounds of one or more metals from Group 10 on the periodic table, or mixtures thereof (L) one or more metals from Group 10 on the periodic table, one or more compounds of one or more metals from Group 10 on the periodic table, or mixtures thereof, per gram of catalyst from 0.0001 to 0.6 grams or from 0.001 to 0.3 grams (M) vanadium, one or more compounds of vanadium, or mixtures thereof, (n) nickel, one or more compounds of nickel, or mixtures thereof, and (o) one of cobalt, cobalt (P) 0.001 to 0.3 grams or 0.005 to 0.1 grams of molybdenum per gram of catalyst, comprising (p) one or more compounds of molybdenum, molybdenum, or mixtures thereof; One or more molybdenum compounds, or mixtures thereof, (r) one or more compounds of tungsten, tungsten, or mixtures thereof, and (s) 0.001 to 0.3 grams of tongue per gram of catalyst (T) one or more metals from Group 6 on the periodic table, one or more metals from Group 10 on the periodic table, having a stainless steel, one or more tungsten compounds, or mixtures thereof, wherein the Group 10 metals to the Group 6 metals The molar ratio of is in the range of 1 to 5 and includes (u) one or more elements from group 15 of the periodic table, one or more compounds of one or more elements from group 15 of the periodic table, or mixtures thereof ( v) one or more elements from group 15 on the periodic table of 0.00001 to 0.06 grams per gram of the catalyst, one or more compounds of one or more elements from group 15 on the periodic table, or mixtures thereof, (w) porous, porous One or more compounds, or mixtures thereof, (x) with up to 0.1 grams of alpha alumina per gram of catalyst, and / or (y) at least 0.5 grams of theta egg per gram of catalyst It provides a method having a mina.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to combine a carrier comprising theta alumina with one or more metals to form a carrier / metal mixture, theta alumina Providing a process for shaping a catalyst comprising heat treating the carrier / metal mixture at a temperature of at least 400 ° C., which method comprises: (a) combining the carrier / metal mixture with water to form a paste and extruding the paste; (b) heat treating the alumina at a temperature of at least 800 ° C. to obtain theta alumina and / or (c) sulfiding the catalyst.

The present invention, in some embodiments, comprises combining one or more methods or compositions according to the present invention to contact a crude oil feed with one or more catalysts, wherein at least one of the catalysts in this method The pore size distribution of the catalyst of (a) is at least 60Å, at least 90Å, at least 180Å, at least 200Å, at least 230Å, at least 300Å, up to 230Å, up to 500Å, or 90 to 180Å, 100 to 140Å, 120 to 130Å, 230 Having an average pore diameter in the range of ˜250 mm, 180-500 mm, 230-500 mm, or 60-300 mm, (b) at least 60% of the total number of voids has a pore diameter within 45 mm, 35 mm, 25 mm , (c) at least 60 m ² / g, at least 90 m ² / g, at least 100 m ² / g, at least 120 m ² / g, at least 150 m ² / g, at least 200 m ² / g, or at least 220 m Has a surface area of ² / g and / or (d) at least 0.3 cm ³ / g, at least 0.4 cm ³ / g, at least 0.5 cm ³ / g, or at least 0.7 cm ³ / g Has a total volume of all pores.

The present invention, in some embodiments, comprises combining one or more methods or compositions according to the present invention to contact a crude oil feed with one or more catalysts, the catalyst comprising: (a) alumina, Silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof, and / or zeolites, (b) comprising gamma alumina and / or delta alumina, (c) at least 0.5 per gram carrier Grams of gamma alumina, (d) at least 0.3 grams or at least 0.5 grams of theta alumina, per gram of carrier, (e) alpha alumina, gamma alumina, delta alumina, theta alumina, or mixtures thereof, (f) up to 0.1 grams of alpha alumina per gram of carrier.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide a vanadium catalyst, which (a) provides a pore size distribution having an average pore diameter of at least 60 mm 3. And (b) a carrier comprising theta alumina, wherein the vanadium catalyst has an average pore diameter of at least 60 μs, and (c) one or more metals from Group 6 on the periodic table, one or more from Group 6 on the periodic table. One or more compounds of metals, or mixtures thereof, and / or (d) at least one metal from Group 6 on the periodic table, at least one metal from Group 6 on the periodic table, per gram of catalyst One or more compounds, or mixtures thereof.

 The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide a crude oil product, the crude oil product comprising (a) at most 0.1, 0.001-0.5, 0.01-0.2, or TAN of 0.05 to 0.1, (b) alkali and alkaline earth metals in metal salts of up to 0.000009 grams of organic acid per gram of crude oil product, (c) up to 0.00002 grams of Ni / V / Fe per gram of crude oil product, and / or (d ) Have at least one of the above catalysts greater than 0 grams per gram of crude oil product but less than 0.01 grams.

 The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or mixtures thereof. , Wherein (a) at least one of the alkali metals is lithium, sodium, or potassium, and / or (b) at least one of the alkaline earth metals is magnesium or calcium.

 The present invention, in some embodiments, comprises contacting the crude feed with one or more catalysts to combine one or more methods or compositions according to the present invention to produce a final product comprising the crude product. A process comprising the steps of: (a) combining the crude oil product with the crude oil feed or with other crude oil to form a formulation suitable for transfer, (b) synthesizing the crude oil product with the crude oil feed Or blending with other crude oil to form a blend suitable for processing equipment, (c) classifying the crude product, and / or (d) separating the crude product into one or more distillates, and the middle streams. Producing a fuel for transportation from at least one of the.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide a supported catalyst composition, which composition comprises (a) at least 0.3 grams or at least 0.5 grams per gram of carrier; Has a theta alumina, (b) comprises delta alumina in the carrier, (c) a maximum of 0.1 grams of alpha alumina per gram of carrier, (d) has a pore size distribution with an average pore diameter of at least 230 mm 3, and (e ) Has a pore volume with a pore size distribution of at least 0.3 cm ³ / g or at least 0.7 cm ³ / g, (f) has a surface area of at least 60 m ² / g or at least 90 m ² / g, and (g) on the periodic table One or more metals from Groups 7-10, one or more compounds of one or more metals from Groups 7-10 on the periodic table, or mixtures thereof, (h) one or more metals from Group 5 on the periodic table, Five groups on the periodic table One or more compounds of one or more metals, or mixtures thereof, comprising: (i) one or more metals from Group 5 on the periodic table of 0.0001 to 0.6 grams or 0.001 to 0.3 grams per gram of catalyst, group 5 on the periodic table Having one or more compounds of one or more metals from, or mixtures thereof, (j) one or more metals from group 6 on the periodic table, one or more compounds of one or more metals from group 6 on the periodic table, or their Mixtures comprising (k) one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or a gram of 0.0001 to 0.6 grams or 0.001 to 0.3 grams per gram of catalyst Mixtures comprising (l) vanadium, one or more compounds of vanadium, or mixtures thereof, (m) molybdenum, one or more of molybdenum Combinations, or mixtures thereof, (n) one or more compounds of tungsten, tungsten, or mixtures thereof, and (o) one or more compounds of cobalt, cobalt, or mixtures thereof And / or (p) nickel, one or more compounds of nickel, or mixtures thereof.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide a crude oil composition, wherein the crude oil composition comprises (a) a TAN of at most 1, at most 0.5, at most 0.3 or at most 0.1. (B) a minimum of 0.001 gram of hydrocarbon having a boiling range distribution of 95 ° C. to 260 ° C. at 0.101 MPa per gram of composition, and a minimum of 0.001 gram of hydrocarbon having a boiling range distribution of 260 ° C. to 320 ° C. at 0.101 MPa 0.005 grams, or at least 0.01 grams, at least 0.001 grams of hydrocarbons having a boiling range distribution from 320 ° C. to 650 ° C. at 0.101 MPa, (c) at least 0.0005 grams of base nitrogen per gram of composition, and (d) at least per gram of composition 0.001 gram or at least 0.01 gram total nitrogen and / or (e) up to 0.00005 gram total nickel and vanadium per gram composition.

The present invention, in some embodiments, combines one or more methods or compositions according to the present invention to provide a crude oil composition, wherein the crude oil composition comprises one or more catalysts, wherein at least one of these catalysts is (a) has a pore size distribution having an average pore diameter in the range of at least 180 Å, at most 500 Å, and / or 90 to 180 Å, 100 to 140 Å, 120 to 130 Å, (b) having a mean pore diameter of at least 90 Å, More than 60% of the total pore size in the pore size distribution has a pore diameter within 45Å, 35Å, or 25Å of average pore diameter, and (c) at least 100 m ² / g, at least 120 m ² / g, or at least 220 m Has a surface area of ² / g and (d) comprises a carrier, which comprises alumina, silica, silica alumina, titanium oxide, zirconium oxide, magnesium oxide, zeolite and / or mixtures thereof and (e) One or more metals from Groups 5-10 on the periodic table, one or more compounds of one or more metals from Groups 5-10 on the periodic table, or mixtures thereof, and (f) one or more from Group 5 on the periodic table Metals, one or more compounds of one or more metals from Group 5 on the periodic table, or mixtures thereof, and (g) at least 0.0001 grams of one or more Group 5 metals, one or more Group 5 metal compounds per gram of catalyst Or (h) one or more metals from Group 6 on the periodic table, one or more compounds of one or more metals from Group 6 on the periodic table, or mixtures thereof; At least 0.0001 grams of one or more Group 6 metals, one or more Group 6 metal compounds, or mixtures thereof, (j) one or more metals from Group 10 on the periodic table, One or more compounds of one or more metals from Group 10 on the periodic table, or mixtures thereof, and / or (k) one or more elements from Group 15 on the periodic table, one or more elements from Group 15 on the periodic table One or more compounds of these, or mixtures thereof.

In other embodiments, features of certain embodiments of the invention can be combined with features of other embodiments of the invention. For example, features from one embodiment of the present invention can be combined with any of the other embodiments.

In other embodiments, the crude oil product can be obtained by any of the methods and systems described herein.

In other embodiments, additional features may be added to the specific embodiments described herein.

Those skilled in the art will appreciate the advantages of the present invention with reference to the following detailed description and accompanying drawings.

1 is a schematic diagram showing one embodiment of a contact system.

2A and 2B are schematic diagrams showing embodiments of a contact system including two contact regions.

3A and 3B are schematic diagrams showing embodiments of a contact system including three contact regions.

4 is a schematic diagram showing one embodiment of a separation area in combination with a contact system.

5 is a schematic diagram showing one embodiment of a blending region in combination with a contact system.

6 is a schematic diagram showing one embodiment of a combination of a separation zone, a contact system, and a blending zone.

FIG. 7 is a diagram showing representative characteristics of a crude oil feed and a crude oil product in one embodiment where the crude oil feed is contacted with three catalysts.

FIG. 8 is a graph showing a weighted average bed temperature versus run time in one embodiment where a crude feed is contacted with one or more catalysts.

FIG. 9 is a diagram showing representative characteristics of the crude oil feed and the crude oil product in one embodiment where the crude oil feed is contacted with two catalysts.

FIG. 10 is another diagram showing representative characteristics of the crude oil feed and the crude oil product in one embodiment where the crude oil feed is contacted with two catalysts.

FIG. 11 is a diagram showing representative characteristics of a crude feed and crude product in embodiments where the crude feed is contacted with four different catalyst systems.

FIG. 12 is a graph showing the P-value of crude product over run time in embodiments where the crude feed is contacted with four different catalyst systems.

FIG. 13 is a graph showing net hydrogen uptake by the crude oil feed versus run time in embodiments where the crude oil feed is contacted with four different catalyst systems.

FIG. 14 is a graph showing residue content in crude product as a percentage by weight versus run time in embodiments where the crude feed is contacted with four different catalyst systems.

FIG. 15 is a graph showing changes in API specific gravity of crude product over run time in embodiments in which the crude feed is contacted with four different catalyst systems.

FIG. 16 is a graph showing the oxygen content in crude oil products as a percentage by weight versus run time in embodiments where the crude oil feed is contacted with four different catalyst systems.

FIG. 17 illustrates embodiments of contacting a crude oil feed with catalyst systems comprising various molybdenum catalyst amounts and vanadium catalyst amounts, catalyst systems including vanadium catalysts and molybdenum / vanadium catalysts, and glass beads, This chart shows the typical properties of crude oil feeds and crude oil products.

FIG. 18 is a diagram showing characteristics of a crude oil feed and a crude oil product in embodiments in which the crude oil feed is contacted with one or more catalysts at various liquid hourly space velocities.

FIG. 19 is a diagram showing the properties of a crude feed and crude product in embodiments where the crude feed is contacted at various contact temperatures.

The invention can accommodate various modifications and variations, and the drawings show specific embodiments thereof. The drawings may not be to scale. The drawings and detailed description are not intended to limit the invention to the particular forms disclosed above, on the contrary, the intention is to cover all modifications falling within the spirit and scope of the invention as defined by the appended claims, It is intended to include equivalents and substitutes.

Herein, embodiments of the present invention will be described in more detail. Definitions of terms used herein are as follows.

"ASTM" means the American Society for Materials and Testing.

"API gravity" refers to API gravity at 15.5 ° C (60 ° F). API specific gravity is as defined by ASTM specification D6822.

The atomic hydrogen percentage and atomic carbon percentage of crude oil feed and crude oil product are as defined by ASTM specification D5291.

Boiling range distributions for crude oil feeds, final products, and / or crude oil products are as defined by ASTM specification D5307, unless otherwise noted.

"C ₅ Asphaltenes "means asphaltenes that do not dissolve in pentane. C ₅ The asphaltene content is as defined by ASTM specification D2007.

"Group X metal (s)" refers to one or more compounds of one or more metals of Group X on the periodic table and / or one or more metals of one or more metals of Group X on the periodic table, where X is a group number (eg, 1 on the periodic table) 12). For example, "Group 6 metal (s)" refers to one or more compounds of one or more metals from Group 6 on the periodic table and / or one or more metals from Group 6 on the periodic table.

"Group X element (s)" refers to one or more elements of one or more elements of group X on the periodic table and / or one or more compounds of one or more elements of group X on the periodic table, where X is a group number (eg, 13 18). For example, “Group 15 element (s)” refers to one or more compounds of one or more elements from group 15 of the periodic table and / or one or more elements from group 15 of the periodic table.

Within the scope of the present application, the weight of the metal from the periodic table, the weight of the compound of the metal from the periodic table, the weight of the element from the periodic table or the weight of the compound of the element from the periodic table are calculated according to the weight of the metal or the weight of the element. . For example, 0.1 gram of MoO ₃ per gram of catalyst Using, the calculated weight of molybdenum metal in the catalyst is 0.067 grams per gram of catalyst.

"Content" refers to the weight of one component in a substrate, expressed as parts by weight or percentage by weight relative to the total weight of the substrate (eg, crude feed, final product, or crude product). "wtppm" refers to only one hundredth of the weight.

"Crude oil feed / final product mixture" refers to a mixture that comes into contact with the catalyst during processing.

"Distillate" refers to a hydrocarbon having a boiling range distribution between 204 ° C. (400 ° F.) and 343 ° C. (650 ° F.) at 0.101 MPa. Distillate content is as defined by ASTM specification D5307.

"Heteroatoms" refer to oxygen, nitrogen, and / or sulfur included in the molecular structure of a hydrocarbon. The heteroatom content is as defined by ASTM specification E385 for oxygen, D5762 for total nitrogen, and D4294 for sulfur. "Total basic nitrogen" refers to nitrogen compounds having a pKa of less than 40. Base nitrogen ("bn") is as defined by ASTM specification D2896.

A "hydrogen source" refers to hydrogen, and / or compounds and / or compounds that provide hydrogen to the compound (s) in the crude oil feed when the crude oil feed reacts with the catalyst. Hydrogen sources may include, but are not limited to, hydrocarbons (eg, C ₁ -C ₄ hydrocarbons such as methane, ethane, propane, butane), water, or mixtures thereof. Mass balance can be analyzed to estimate the net amount of hydrogen provided to the compound (s) in the crude oil feed.

"Flat plate crush strength" refers to the compressive force required to break a catalyst. Plate breaking strength is as defined by ASTM standard D4179.

"LHSV" refers to the ratio of the liquid volume supplied per hour (h ^-1 ) to the total volume of the catalyst. The total volume of catalyst is calculated by summing all catalyst volumes in the contacting zones, as described herein.

"Liquid mixture" refers to a composition comprising one or more compounds in liquid phase at standard temperature and standard pressure (25 ° C., 0.101 Mpa, hereinafter referred to as “STP”), or one or more compounds in liquid phase and STP in STP. Refers to a composition comprising a combination of one or more compounds in the solid phase.

"Periodic Table" means the periodic table established by the International Union of Pure and Applied Chemistry in November 2003.

"Metal in organic acid metal salt" refers to alkali metal, alkaline earth metal, zinc, arsenic, chromium or combinations thereof. The content of metals in the organic acid metal salt is as defined by ASTM specification D1318.

The "Micro-Carbon Residue" ("MCR") content refers to the amount of residual carbon remaining after evaporation and pyrolysis of the substrate. MCR content is as defined by ASTM specification D4530.

“Naphtha” refers to hydrocarbon components having a boiling range distribution between 38 ° C. (100 ° F.) and 200 ° C. (392 ° F.), at 0.101 MPa. Naphtha content is as defined by ASTM specification D5307.

"Ni / V / Fe" refers to nickel, vanadium, iron or combinations thereof.

"Ni / V / Fe content" refers to the content of nickel, vanadium, iron or combinations thereof. This Ni / V / Fe content is as defined by ASTM standard D5708.

"Nm ³ / m ³ " refers to the normal cubic meter of gas per cubic meter of crude oil feed.

"Non-carboxyl group-containing organic oxygen compounds" refers to organic oxygen compounds that do not have a carboxy (-CO _2- ) group. Non-carboxyl group-containing organic oxygen compounds include, but are not limited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof that do not have a carboxyl group.

"Non-condensable gas" refers to components and / or mixtures of components that are gases in STP.

A "peptization" value, ie "P-value", refers to a value that shows the aggregation of asphaltenes in a crude oil feed. The method of determining this P-value is J.J. "Measurement and Importance of Asphalt Bridges" by J. J. Heithaus, Journal of Institute of Petroleum, Vol. 48, 458, February 1962, pages 45-53.

"Pore diameter", "average pore diameter", and "pore volume" are pore diameters, averages as determined by ASTM specification D4284 (mercury porosimetry using mercury infiltration at a contact angle equivalent to 140 °). Pore diameter, and pore volume. To obtain these values, the Micromeritics ^® A9220 instrument (Micromeritics Inc., Norcross, Georgia, USA) can be used.

"Residue" refers to components that have a boiling range distribution of temperatures higher than 538 ° C (1000 ° F), as defined by ASTM specification D5307.

"SCFB" refers to the standard cubic feet of gas per barrel of crude oil feed.

The "surface area" of the catalyst is as defined by ASTM Standard D3663.

"TAN" refers to the total acid value expressed in milligrams ("mg") of KOH per gram ("g") of sample. TAN is as defined by ASTM specification D664.

"VGO" refers to hydrocarbons having a boiling range distribution between 343 ° C (650 ° F) and 538 ° C (1000 ° F) at 0.101 MPa. VGO content is as defined by ASTM specification D5307.

“Viscosity” refers to kinematic viscosity at 100 ° F. at 37.8 ° C. Viscosity is as determined using ASTM specification D445.

In the present application, if the values obtained for the properties of the substrate being tested are outside of the limits of the test method, those properties can be tested by modifying and / or recalibrating the test method.

Crude may be prepared and / or distilled from hydrocarbon containing formations and then stabilized. The crude contains crude oil. Crude oil is typically a solid, semi-solid, and / or liquid. Stabilization treatment includes, but is not limited to, removing non-condensable gases, water, salt, or combinations thereof from crude oil to form stabilized crude oil. This stabilization is usually done at or near the site of manufacture and / or distillation.

Stabilized crude oil is typically not distilled and / or fractionally distilled in a treatment facility for producing a number of components (eg, naphtha, distillate, VGO, and / or lubricants) having a specific boiling range distribution. . Distillation includes atmospheric distillation methods and / or vacuum distillation methods, but is not limited to these methods. Undistilled and / or fractionated stabilized crude oil may comprise components having more than 4 carbons in an amount of at least 0.5 grams per gram of crude oil. Examples of stabilized crude oils include whole crudes, topped crudes, desalted crudes, desalted topped crudes, or combinations thereof. "Topped" refers to crude oil that has been treated to remove at least some of the components having a boiling point of less than 35 ° C. (less than 95 ° F. at 1 atm) at 0.101 MPa. Typically, atmospheric distillate crude oil will have these components in an amount of up to 0.1 grams, up to 0.05 grams, or up to 0.02 grams per gram of the atmospheric distillation crude oil.

Some stabilized crude oils have the property of allowing the stabilized crude oil to be transferred to conventional processing facilities by a transfer carrier (eg, pipeline, truck, or ship). Other crude oils have more than one nonconforming characteristic that imposes barriers. Lower crude oils may not be suitable for transfer carriers and / or processing facilities, resulting in lower economic value of the lower crude oils. Its economic value is the same in reservoirs containing lower crude oil, which are expensive to manufacture, transport and / or process.

Characteristics of lower crude oils include: a) a TAN of at least 0.1 and at least 0.3; b) a viscosity of at least 10 cSt; c) API gravity of up to 19; d) at least 0.00002 grams total Ni / V / Fe content or at least 0.0001 grams Ni / V / Fe per gram crude oil; e) total heteroatom content including at least 0.005 grams of heteroatoms per gram of crude oil; f) residue content comprising at least 0.01 gram residue per gram crude oil; g) a C ₅ asphaltene content comprising at least 0.04 grams C ₅ asphaltenes per gram of crude oil; h) an MCR content comprising at least 0.002 grams MCR per gram crude oil; i) metal content in an organic acid metal salt comprising at least 0.00001 grams of metal per gram of crude oil, or j) combinations thereof, but is not limited thereto. In some embodiments, the lower crude oil may comprise at least 0.2 grams residue, at least 0.3 grams residue, at least 0.5 grams residue, or at least 0.9 grams residue per gram of crude oil. In certain embodiments, the lower crude oil may have a TAN in the range of 0.1 or 0.3-20, 0.3 or 0.5-10, or 0.4 or 0.5-5. In certain embodiments, the lower crude oil may have a sulfur content of at least 0.005 grams, at least 0.01 grams, or at least 0.02 grams per gram of lower crude oil.

In some embodiments, the lower crude oil may comprise a) a TAN of at least 0.5; b) an oxygen content comprising at least 0.005 grams of oxygen per gram of crude oil feed; c) at least 0.04 grams C ₅ per gram crude oil feed C ₅ containing asphaltenes Asphaltene content; d) a viscosity higher than the required viscosity (eg, greater than 10 cSt for a crude oil feed with an API gravity of at least 10); e) metal content in organic acid metal salts of at least 0.00001 grams per gram of crude oil; Or f) may include any combination thereof, but is not limited thereto.

Lower crude oils have a boiling range distribution of at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, and 0.101 MPa at 200 ° C to 300 ° C for hydrocarbons having a boiling range distribution of 0.101 MPa to 95 ° C to 200 ° C per gram of lower crude oil. Hydrocarbons having a boiling range distribution of at least 0.01 grams, at least 0.005 grams, or at least 0.001 grams, and 0.101 MPa at a boiling range of 300 ° C. to 400 ° C., at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, and 0.101 MPa Hydrocarbons having a boiling range distribution of 400 ° C.-650 ° C. may comprise at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams.

Lower crude oils have a boiling range distribution of at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams, 0.101 MPa at 100 ° C. to 200 ° C. for hydrocarbons having a boiling range distribution of 0.101 MPa or less at 100 ° C. per gram of lower crude oil. At least 0.001 gram, at least 0.005 gram, or at least 0.01 gram of hydrocarbon, at least 0.001 gram, at least 0.005 gram, or at least 0.01 gram, at 300 ° C. at 0.101 MPa for hydrocarbons having a boiling range distribution of 200 ° C. to 300 ° C. at 0.101 MPa. At least 0.001 gram, at least 0.005 gram, or at least 0.01 gram of hydrocarbon having a boiling range distribution of 400 ° C., and at least 0.001 gram, at least 0.005 gram, or minimum of hydrocarbon having a boiling range distribution of 400 ° C. to 650 ° C. at 0.101 MPa. May contain 0.01 grams.

Some lower crude oils may contain at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams per gram of lower crude oil, in addition to those boiling components having a higher boiling range distribution, having a boiling range distribution of less than 100 ° C. at 0.101 MPa. Can be. Typically, the lower crude oil has such hydrocarbons up to 0.2 grams or up to 0.1 grams per gram of lower crude oil.

Some lower crude oils may contain at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons having a boiling range distribution of at least 200 ° C. above 0.101 MPa per gram of lower crude oil.

Some lower crude oils may contain at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons per gram of lower crude oil having a boiling range distribution of at least 650 ° C.

Lower crude oils that can be processed using the treatment processes described here include the following regions of the world: the US Gulf Coast and Southern California, Canadian Tar Sands, Brazil Santos and Campos Basin, Suezman Egypt, Chad, For example, crude oil from the North Sea of England, the coast of Angola, Bohai Bay, China, Zulia, Venezuela, Malaysia and Sumatra, Indonesia.

Processing lower crude oil can improve the properties of the lower crude oil to be suitable for transport and / or processing.

Crude oil and / or lower crude oil processed here is referred to as "crude oil feed". This crude oil feed can be topped as described herein. Crude oil products typically obtained by treating crude oil feeds are suitable for conveying and / or treating, as described herein. The properties of the crude oil product produced as described herein are closer to the corresponding properties of West Texas light oil or Brant oil than the crude oil feed, thereby enhancing the economic value of the crude oil feed. Since such crude oil products can be purified with less pretreatment or without any pretreatment, the purification efficiency can be improved. The pretreatment may include atmospheric distillation to remove desulfurization, demetallization and / or impurities.

Treatment of the crude oil feed according to the invention described herein may comprise contacting the crude oil feed with the catalyst (s) in one contacting region and / or a combination of two or more contacting regions. In one contacting zone, at least one characteristic of the crude oil feed may be altered by contact with one or more catalysts related to that same characteristic of the crude oil feed. In some embodiments, the contact is performed in the presence of a hydrogen source. In certain embodiments, the hydrogen source is one or more hydrocarbons that react under predetermined contact conditions to supply relatively small amounts of hydrogen to the compound (s) in the crude oil feed.

1 is a schematic view of a contact system 100 that includes a contact region 102A, where the crude oil feed enters the contact region 102 through the conduit 104. The contact region may be a reactor, one location of the reactor, a plurality of locations of the reactor, or a combination thereof. Examples of contact areas include stacked bed reactors, fixed bed reactors, ebullating bed reactors, continuous stirred tank reactors ("CSTR"), fluidized bed reactors, spray reactors And liquid / liquid contactors. In some embodiments, the contact system is at or connected to an offshore facility. The contact between the crude oil feed and the catalyst (s) in the contact system 100 may be a continuous process or a batch process.

The contacting zone may comprise one or more catalysts (eg two catalysts). In some embodiments, contacting the first of the two catalysts with the crude oil feed can lower the TAN of the crude feed. Subsequent contact of the crude oil feed with lower TAN to the second catalyst may result in lower heteroatomic content and higher API specific gravity. In other embodiments, the combination of these properties of TAN, viscosity, Ni / V / Fe content, heteroatomic content, residue content, API specific gravity, or crude oil product may be achieved by contacting the crude oil feed with one or more catalysts. Thereafter, it changes by at least 10% with respect to the same properties of the crude oil feed.

In some embodiments, the volume of catalyst in the contacting zone is in the range of 10 to 60 volume percent, 20 to 50 volume percent, or 30 to 40 volume percent of the total volume of the crude oil feed in the contacting region. In certain embodiments, the slurry of catalyst and crude oil feed in the contacting zone may comprise 0.001-10 grams, 0.005-5 grams, or 0.01-3 grams of catalyst per 100 grams of crude oil feed.

Contact conditions in the contacting zone may include, but are not limited to, temperature, pressure, hydrogen source flow, crude oil feed flow, or a combination thereof. In some embodiments, the contact conditions are controlled to produce a crude oil product having certain properties. The temperature in the contact region can vary in the range of 50-500 ° C, 60-440 ° C, 70-430 ° C, or 80-420 ° C. The pressure in the contact zone can vary in the range of 0.1-20 MPa, 1-12 MPa, 4-10 MPa, or 6-8 MPa. Crude oil feed LHSV is typically 0.1 ~ 30h ^-1, can be varied in the range of ^{0.5 ~ 25h -1, 1 ~ 20h} -1, 1.5 ~ 15h -1, or 2 ~ 10h ^-1. In some embodiments, the LHSV is at least 5h ^-1 , at least 11h ^-1 , at least 15h ^-1 , or at least 20h ^{- 1} .

In embodiments in which the hydrocarbon source is supplied as a gas (eg hydrogen gas), the ratio of the gaseous hydrogen source to the crude oil feed in contact with the catalyst (s) is typically 0.1-100,000 Nm ³ / m ^3. Fluctuations in the range 0.5 to 10,000 Nm ³ / m ³ , 1 to 8,000 Nm ³ / m ³ , 2 to 5,000 Nm ³ / m ³ , 5 to 3,000 Nm ³ / m ³ , or 10 to 800 Nm ³ / m ³ do. The hydrogen source, in some embodiments, engages with the carrier gas (es) to circulate the contacting region. The carrier gas can be, for example, nitrogen, helium, and / or argon. This carrier gas may promote the flow of crude oil feed and / or the flow of hydrogen source in the contacting zone (s). This carrier gas may improve mixing in the contacting region (s). In some embodiments, a hydrogen source (eg, hydrogen, methane, or ethane) may be used as the carrier gas to circulate the contacting zone.

The hydrogen source may enter the contact region 102 co-currently with the crude oil feed in conduit 104 or separately via conduit 106. In the contacting region 102, the contact of the catalyst with the crude oil feed produces a crude product and, in some embodiments, a final product comprising gas. In some embodiments, the carrier gas is combined in conduit 106 with the crude oil feed and / or the hydrogen source. The final product may exit contact region 102 and enter separation region 108 via conduit 110.

In the separation zone 108, generally known separation techniques, such as gas-liquid separation, can be used to separate the crude oil product and gas from the final product. The crude product may exit the separation zone 108 and pass through the conduit 112 and then be transferred to transfer carriers, pipelines, storage vessels, refineries, other processing areas, or a combination thereof. The gas may include gases formed during processing (eg, hydrogen sulfide, carbon dioxide, and / or carbon monoxide), excess gaseous hydrogen source, and / or carrier gas. Excess gas may be refluxed into the contact system 100, purified, and transferred to other process areas, storage vessels, or a combination thereof.

In some embodiments, contacting the crude oil feed with the catalyst (s) to produce the final product is performed in two or more contacting zones. The final product can be separated to form crude oil product and gas (s).

2 and 3 are schematic diagrams showing embodiments of a contact system 100 that includes two or three contact regions. 2A and 2B, the contact system 100 includes a contact region 102 and a contact region 114. 3A and 3B include contact regions 102, 114, and 116. 2A and 3A, contact regions 102, 114, 116 are depicted as independent contact regions within a reactor. Crude feed enters the contact region 102 via the conduit 104.

In some embodiments, the carrier gas is combined in the conduit 106 with the hydrogen source and introduced into the contact regions as a mixture. In some embodiments, as shown in FIGS. 1, 3A, and 3B, the hydrogen source and / or carrier gas may enter the one or more contacting areas separately with the crude oil feed via conduit 106 and / or Or, for example, through conduit 106'to enter one or more contacting regions in a direction opposite to the flow of the crude feed. The addition of a hydrogen source and / or carrier gas to oppose the flow of the crude oil feed may improve the mixing and / or contact of the crude oil feed with the catalyst.

Contacting the crude oil feed with the catalyst (s) in the contacting zone 102 forms a feed stream. This feed stream flows from the contact region 102 to the contact region 114. 3A and 3B, the feed stream flows from contact region 114 to contact region 116.

Contact regions 102, 114, 116 may include one or more catalysts. As shown in FIG. 2B, the feed stream exits the contact region 102 and enters the contact region 114 via the conduit 118. As shown in FIG. 3B, the feed stream exits the contact region 114 and enters the contact region 116 via the conduit 118.

The feed stream may contact additional catalyst (s) in contact region 114 and / or contact region 116 and form the final product. The final product exits contact region 114 and / or contact region 116 and enters isolation region 108 via conduit 110. Crude oil product and / or gas (s) are separated from the final product. The crude product exits separation zone 108 through conduit 112.

4 is a schematic diagram showing one embodiment of a separation zone upstream of the contact system 100. Lower crude oil (with or without atmospheric distillation) enters separation zone 120 via conduit 122. In separation zone 120, at least a portion of the lower crude oil is separated using techniques known in the art (eg, sparging, membrane separation, decompression) to produce a crude oil feed. do. For example, water can be at least partially separated from the lower crude oil. In another embodiment, components having a boiling range distribution below 95 ° C. or 100 ° C. may be at least partially separated from the lower crude oil to produce a crude oil feed. In certain embodiments, at least some of the naphtha and at least some of the more volatile compounds than naphtha can be separated from the lower crude oil. In some embodiments, at least some of the separated components exit separation region 120 through conduit 124.

The crude oil feed obtained from separation zone 120 may, in some embodiments, comprise a mixture of components having a boiling range distribution of at least 100 ° C. or, in some embodiments, a boiling range distribution of at least 120 ° C. or higher. And mixtures of components having. Typically, the separated crude oil feed comprises a mixture of components having a boiling range distribution of 100-1,000 ° C, 120-900 ° C, or 200-800 ° C. At least a portion of the crude oil feed exits separation zone 120, passes through conduit 126, into contact system 100 (see, for example, the contact zones of FIGS. 1-3) and is processed to form a crude product. . In some embodiments, separation region 120 may be located upstream or downstream of a desalting unit. After the treatment, the crude product exits the contact system 100 through the conduit 112.

In certain embodiments, the crude product is combined with crude oil that is the same as or different from the crude feed. For example, the crude oil product can be combined with crude oil of different viscosity, thus obtaining a blended product having a viscosity between the viscosity of the crude oil product and the viscosity of the crude oil. In another embodiment, the crude product may be combined with crude oil having a different TAN, thus obtaining a product having a TAN between the TAN of the crude product and the TAN of the crude oil. The blended product may be suitable for transport and / or processing.

As shown in FIG. 5, in some embodiments, the crude oil feed enters the contact system 100 through the conduit 104 and at least a portion of the crude product passes through the contact system 100 through the conduit 128. Me and introduced into the blending region 130. In blending zone 130, at least a portion of the crude oil product is one or more process streams (eg, a hydrocarbon stream such as naphtha produced by separating one or more crude oil feeds), crude oil, crude oil feed, or mixtures thereof It is combined with to obtain a blended product. The process stream, crude feed, crude oil, or mixtures thereof are introduced directly into blending zone 130 or upstream of the blending zone via conduit 132. The mixing system can be disposed in or near the blending region 130. The blended product may meet product specifications and / or requirements of transfer carriers as defined by the refinery. Product specifications include, but are not limited to, API specific gravity, TAN, viscosity, or ranges or limitations thereof. The blended product exits or is processed through the conduit 134 out of the blending region 130.

In FIG. 6, the lower crude oil enters separation zone 120 through conduit 122 and is separated as described above to form a crude oil feed. The crude oil feed then enters contact system 100 via conduit 126. At least some of the components from the lower crude oil exit separation area 120 through conduit 124. At least a portion of the crude product exits contact system 100 and enters blending region 130 through conduit 128. Other process streams and / or crude oil enter the blending region 130 directly or via conduit 132 to combine with the crude product to form the blended product. This blend product exits blend zone 130 through conduit 134.

In some embodiments, the crude oil and / or blended product is sent to a refinery and / or treatment facility. The crude oil product and / or blended product may be processed to produce products such as transportation fuels, heating fuels, lubricants, or chemicals. The treatment may comprise distilling and / or partial distillation of the crude oil and / or blended product to obtain one or more distillates. In certain embodiments, the crude oil product, the blended product and / or the one or more distillates may be hydrotreated.

In some embodiments, the crude oil product has a TAN of at most 90%, at most 50%, at most 30%, or at most 10% of the TAN of the crude oil feed. In certain embodiments, the crude oil product has a TAN in the range of 1-80%, 20-70%, 30-60%, or 40-50% of the TAN of the crude feed. In certain embodiments, the crude oil product has a TAN of at most 1, at most 0.5, at most 0.3, at most 0.2, at most 0.1, or at most 0.05. The crude oil product's TAN is usually at least 0.0001 and in many cases at least 0.001. In certain embodiments, the TAN of the crude oil product is in the range of 0.001-0.5, 0.01-0.2, or 0.05-0.1.

In certain embodiments, the total Ni / V / Fe content of the crude product is at most 90%, at most 50%, at most 10%, at most 5%, or at most 3% of the Ni / V / Fe content of the crude feed. Becomes In certain embodiments, the total Ni / V / Fe content of the crude product is 1-80%, 10-70%, 20-60%, or 30-50% of the Ni / V / Fe content of the crude feed. Is in the range of. In certain embodiments, the crude oil product is from 1 × 10 ⁻⁷ grams to 5 × 10 ⁻⁵ grams, 3 × 10 ⁻⁷ grams to 2 × 10 ⁻⁵ grams, or 1 × 10 ⁻⁶ per gram of crude oil product It has a total Ni / V / Fe content in the range of grams to 1 × 10 ⁻⁵ grams. In some embodiments, the crude oil has a maximum of 2 × 10 ⁻⁵ grams of Ni / V / Fe. In certain embodiments, the total Ni / V / Fe content of the crude oil product is in the range of 70-130%, 80-120%, or 90-110% of the Ni / V / Fe content of the crude oil feed. .

In certain embodiments, the crude oil product has a total content of metals in an organic acid metal salt of up to 90%, up to 50%, up to 10%, or up to 5% of the total content of metals in the organic acid metal salt of the crude feed. . In certain embodiments, the crude oil product is in an organic acid metal salt in the range of 1-80%, 10-70%, 20-60%, or 30-50% of the total content of metals in the organic acid metal salt of the crude feed. Has a total content of metals. Organic acids that generally form metal salts include, but are not limited to, carboxylic acids, thiols, imides, sulfonic acids, sulfonates, and the like. Carboxylic acids include, but are not limited to, naphthenic acid, phenanthrene acid, benzene acid, and the like. The metal parts of the metal salts include alkali metals (eg lithium, sodium and potassium), alkaline earth metals (eg magnesium, calcium and barium), group 12 metals (eg zinc and cadmium), Group 15 metals (eg, arsenic), Group 6 metals (eg, chromium), or mixtures thereof.

In certain embodiments, the crude oil product is an organic acid metal salt per gram crude oil product, in the range of 0.0000001 grams to 0.00005 grams, 0.0000003 grams to 0.00002 grams, or 0.000001 grams to 0.00001 grams of metals in the organic acid metal salt per gram of crude oil product. Has a total content of metals. In certain embodiments, the total content of metals in the organic acid metal salt of the crude oil product is 70-130%, 80-120%, or 90-110% of the total content of metals in the organic acid metal salt in the crude feed.

In certain embodiments, the API gravity of the crude oil product produced when the crude oil feed is in contact with a catalyst is 70-130%, 80-120%, 90-90% of the API gravity of the crude oil feed under the contact conditions. 110%, or 100-130%. In certain embodiments, the API specific gravity of the crude product is 14-40, 15-30, or 16-25.

In certain embodiments, the crude oil product has a viscosity of at most 90%, at most 80%, or at most 70% of the viscosity of the crude oil feed. In certain embodiments, the crude oil product has a viscosity in the range of 10-60%, 20-50%, or 30-40% of the viscosity of the crude oil feed. In certain embodiments, the viscosity of the crude product is the viscosity of the crude feed with the API specific gravity of the crude product being 70-130%, 80-120%, or 90-110% of the API specific gravity of the crude feed. Is up to 90%.

In certain embodiments, the crude oil product has a total heteroatom content of at most 90%, at most 50%, at most 10%, or at most 5% of the total heteroatom content of the crude feed. In certain embodiments, the crude oil product has a total heteroatom content of at least 1%, at least 30%, at least 80%, or at least 99% of the total heteroatom content of the crude feed.

In certain embodiments, the sulfur content of the crude product may be at most 90%, at most 50%, at most 10%, or at most 5% of the sulfur content of the crude product. In certain embodiments, the crude product has a sulfur content of at least 1%, at least 30%, at least 80%, or at least 99% of the sulfur content of the crude feed. In certain embodiments, the sulfur content of the crude product is 70-130%, 80-120%, or 90-110% of the sulfur content of the crude feed.

In some embodiments, the total nitrogen content of the crude product may be at most 90%, at most 80%, at most 10%, or at most 5% of the total nitrogen content of the crude feed. In certain embodiments, the crude oil product has a total nitrogen content of at least 1%, at least 30%, at least 80%, or at least 99% of the total nitrogen content of the crude feed.

In certain embodiments, the base nitrogen content of the crude oil product may be at most 95%, at most 90%, at most 50%, at most 10%, or at most 5% of the base nitrogen content of the crude feed. In certain embodiments, the crude oil product has a base nitrogen content of at least 1%, at least 30%, at least 80%, or at least 99% of the base nitrogen content of the crude feed.

In some embodiments, the oxygen content of the crude oil product may be at most 90%, at most 50%, at most 30%, at most 10%, or at most 5% of the oxygen content of the crude feed. In certain embodiments, the crude oil product has an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed. In certain embodiments, the oxygen content of the crude product is in the range of 1-80%, 10-70%, 20-60%, or 30-50% of the oxygen content of the crude feed. In certain embodiments, the total content of carboxylic acid compounds of the crude oil product may be up to 90%, up to 50%, up to 10%, up to 5% of the content of carboxylic acid compounds in the crude feed. In certain embodiments, the crude oil product has a total content of at least 1%, at least 30%, at least 80%, or at least 99% of the carboxylic acid compounds in the total content of carboxylic acid compounds in the crude oil feed.

In certain embodiments, selected organic oxygen compounds can be reduced in the crude oil feed. In certain embodiments, the carboxylic acid and / or metal salt of the carboxylic acid can be chemically reduced before the non-carboxyl group containing organic oxygen compounds. Carboxylic acid and non-carboxyl group-containing organic oxygen compounds in crude oil products can be prepared by the use of well-known spectroscopic methods (eg, infrared spectroscopy, mass spectrometry, and / or gas chromatography). Can be identified through analysis.

The crude oil product, in some embodiments, has an oxygen content of at most 90%, at most 80%, at most 70%, or at most 50% of the oxygen content of the crude feed, wherein the TAN of the crude product is Up to 90%, up to 70%, up to 50%, or up to 40% of the TAN of the feed. In some embodiments, the crude oil product has an oxygen content of at least 1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the crude feed, wherein the crude product is Have a TAN of at least 1%, at least 30%, at least 80%, or at least 99% of the TAN.

Additionally, the crude oil product may contain up to 90%, up to 70%, up to 50%, or up to 40% of the carboxylic acid and / or carboxylic acid metal salt content and non-carboxyl group containing organic oxygen of the crude feed. It may have a content of non-carboxyl group containing organic oxygen compounds within 70-130%, 80-120%, or 90-110% of the compounds.

In certain embodiments, the crude oil product contains 0.05-0.15 grams or 0.09-0.13 grams of hydrogen in its own molecular structures per gram of crude oil product. The crude oil product may comprise 0.8-0.9 grams or 0.82-0.88 grams of carbon in its own molecular structures per gram of crude oil product. The ratio (H / C) of atomic hydrogen to atomic carbon of the crude oil product may be within 70-130%, 80-120%, or 90-110% of the atomic H / C ratio of the crude feed. Crude product atom H / C ratios within 10-30% of the crude feed atom H / C ratios indicate that the uptake and / or consumption of hydrogen in the process is relatively low, and / or hydrogen is produced on site Indicates.

The crude oil product contains components having a boiling range. In certain embodiments, the crude oil product comprises at least 0.001 grams or 0.001 to 0.5 grams of hydrocarbons having a boiling range distribution of 0.101 MPa up to 100 ° C. per gram of the crude oil product of 100 ° C. to 200 ° C. at 0.101 MPa. Hydrocarbons having a boiling range distribution of at least 0.001 grams or 0.001 to 0.5 grams, 0.101 MPa to 200 ° C. to 300 ° C. hydrocarbons having a boiling range distribution of at least 0.001 grams or 0.001 to 0.5 grams, 0.101 MPa to 300 ° C. to 400 ° C. At least 0.001 gram or 0.001 to 0.5 grams of hydrocarbons having a boiling range distribution and at least 0.001 grams or 0.001 to 0.5 grams of hydrocarbons having a boiling range distribution of 400 ° C. to 538 ° C. at 0.101 MPa.

In certain embodiments, the crude oil product has a boiling range distribution of 100 ° C. to 200 ° C. at least 0.001 gram and / or 0.101 MPa at least 0.001 gram of hydrocarbon having a boiling range distribution of 0.101 MPa up to 100 ° C. per gram of the crude oil product. At least 0.001 grams of hydrocarbons having

In certain embodiments, the crude oil product may have a minimum of 0.001 grams, or at least 0.01 grams of naphtha, per gram of crude oil product. In other embodiments, the crude oil product may have a naphtha content of up to 0.6 grams, or up to 0.8 grams, per gram of crude oil product.

In certain embodiments, the crude oil product has a distillate content of 70-130%, 80-120%, or 90-110% of the distillate content of the crude oil feed. The distillate content of the crude oil product is in the range of 0.00001 to 0.5 grams, 0.001 to 0.3 grams, or 0.002 to 0.2 grams per gram of crude oil product.

In certain embodiments, the crude oil product has a VGO content of 70-130%, 80-120%, or 90-110% of the VGO content of the crude oil feed. In certain embodiments, the crude oil product has a VGO content in the range of 0.00001 to 0.8 grams, 0.001 to 0.5 grams, 0.002 to 0.4 grams, or 0.001 to 0.3 grams, per gram of crude oil product.

In certain embodiments, the crude oil product has a residue content of 70-130%, 80-120%, or 90-110% of the residue content of the crude oil feed. The crude oil product may have a residue content in the range of 0.00001 to 0.8 grams, 0.0001 to 0.5 grams, 0.0005 to 0.4 grams, 0.001 to 0.3 grams, 0.005 to 0.2 grams, or 0.01 to 0.1 grams per gram of crude oil product. have.

In certain embodiments, the crude oil product has an MCR content of 70-130%, 80-120%, or 90-110% of the MCR content of the crude oil feed, wherein the crude product is C _{And a C 5} asphaltene content of up to 90%, up to 80%, or up to 50% of the ₅ asphaltene content. In some embodiments, C _{5 of} the crude oil feed The asphaltene content is at least 10%, at least 60%, or at least 70% of the C ₅ asphaltene content of the crude feed and the MCR content of the crude product is within 10-30% of the MCR content of the crude feed. In certain embodiments, reducing the C ₅ asphaltene content of the crude feed while maintaining a relatively stable MCR content can increase the stability of the crude feed / final product mixture.

In certain embodiments, the C ₅ asphaltene content and the MCR content can be combined to obtain a mathematical relationship between the high viscosity components in the crude product with respect to the high viscosity components in the crude feed. For example, crude oil feed C ₅ The sum of asphaltene content and crude oil feed MCR content can be expressed as S. Crude Oil C ₅ The sum of the asphaltene content and the crude product MCR content can be expressed as S '. The sums can be compared (S 'to S) to estimate the net decrease in the high viscosity components of the crude oil feed. S 'of the crude product may be in the range of 1-99%, 10-90%, or 20-80% of S. In certain embodiments, the ratio of MCR content of the crude oil product to C ₅ asphaltene content is in the range of 1.0-3.0, 1.2-2.0, or 1.3-1.9.

In certain embodiments, the crude oil product has an MCR content of at most 90%, at most 80%, at most 50%, or at most 10% of the MCR content of the crude feed. In certain embodiments, the crude oil product has an MCR content in the range of 1-80%, 10-70%, 20-60%, or 30-50% of the MCR content of the crude feed. The crude oil product, in certain embodiments, has an MCR of from 0.0001 to 0.1 grams, from 0.005 to 0.08 grams, or from 0.01 to 0.05 grams per gram of crude oil product.

In certain embodiments, the crude product comprises more than 0 grams but less than 0.01 grams, 0.000001 to 0.001 grams, or 0.00001 to 0.0001 grams total catalyst, per gram of crude oil product. The catalyst helps to stabilize the crude oil product during transportation and / or processing. The catalyst prevents corrosion, prevents friction, and / or increases the water separation ability of the crude oil product. The methods described herein may be configured to add one or more catalysts described herein to the crude oil product during processing.

The crude oil product produced in the contact system 100 has different properties from those of the crude oil feed. These characteristics include a) reduced TAN; b) reduced viscosity; c) reduced total Ni / V / Fe content; d) reduced sulfur, oxygen, nitrogen, or a combination thereof; e) reduced residue content; f) reduced C ₅ Asphaltene content; g) reduced MCR content; h) increased API gravity; i) reduced content of metals in the organic acid metal salt; Or j) combinations thereof, but is not limited thereto. In some embodiments, one or more properties of the crude oil product with respect to the crude oil feed can be selectively changed, with other properties being as little or substantially unchanged. For example, it may be desirable to selectively lower only the TAN in the crude oil feed without significantly altering the amount of other components (eg, sulfur, residues, Ni / V / Fe, or VGO). In this way, hydrogen uptake during contact can be "focused" on reducing TAN rather than focusing on reducing other components. Thus, smaller amounts of hydrogen can also be used to reduce other components in the crude oil feed, thus lowering the TAN of the crude oil feed while using smaller amounts of hydrogen. For example, if the lower crude oil has a higher TAN, but the lower crude oil has a sulfur content that can meet the processing and / or transfer specifications, such crude oil feed is more efficiently treated to lower the TAN without reducing sulfur. can do.

Catalysts used in one or more embodiments of the present invention may comprise one or more bulk metals and / or one or more metals on a carrier. These metals may be in elemental form or in the form of compounds of metals. The catalysts described herein can be introduced into the contacting zone as a precursor and then activated as a catalyst in the catalyst zone (eg, crude oil feed comprising sulfur and / or sulfur is contacted with the precursor). The catalyst or combination of catalysts used as described herein may or may not be commercially available catalysts. Examples of commercial catalysts expected to be used as described herein include HDS3 available from CRI International, Inc. (Houston, Texas, U.S.A.); HDS22; HDN60; C234; C311; C344; C411; C424; C344; C444; C447; C454; C448; C524; C534; DN110; DN120; DN130; DN140; DN190; DN200; DN800; DN2118; DN2318; DN3100; DN3110; DN3300; DN3310; RC400; RC410; RN412; RN400; RN420; RN440; RN450; RN650; RN5210; RN5610; RN5650; RM430; RM5030; Z603; Z623; Z673; Z703; Z713; Z723; Z753; And Z763.

In some embodiments, the catalysts used to alter the characteristics of the crude oil feed include one or more Group 5-10 metals on a carrier. Group 5-10 metal (s) include vanadium, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, or mixtures thereof, It is not limited only to these. The catalyst may have a total content of Group 5-10 metal (s) per gram of catalyst, at least 0.0001 grams, at least 0.001 grams, at least 0.01 grams, or 0.0001 to 0.6 grams, 0.005 to 0.3 grams, 0.001 to 0.1 grams, Or a total content of Group 5-10 metal (s) in the range of 0.01-0.08 grams. In some embodiments, the catalyst includes Group 15 element (s) in addition to Group 5-10 metal (s). Examples of group 15 elements include phosphorus. The catalyst may have a total Group 15 element content in the range of 0.000001 to 0.1 grams, 0.00001 to 0.06 grams, 0.00005 to 0.03 grams, or 0.0001 to 0.001 grams per gram of catalyst.

In certain embodiments, the catalyst comprises a Group 6 metal (s). The catalyst may have a total content of Group 6 metal (s) of at least 0.0001 grams, at least 0.01 grams, at least 0.02 grams per gram of catalyst and / or 0.0001 to 0.6 grams, 0.001 to 0.3 grams, 0.005 to 0.1 grams, or May have a total Group 6 metal (s) content in the range of 0.01-0.08 grams. In certain embodiments, the catalyst comprises 0.0001-0.06 grams of Group 6 metal (s) per gram of catalyst. In certain embodiments, the catalyst comprises Group 15 element (s) in addition to Group 6 metal (s).

In certain embodiments, the catalyst comprises a combination of one or more metals and Group 6 metal (s) from Group 5 and / or Groups 7-10. The molar ratio of the Group 6 metal to the Group 5 metal may range from 0.1-20, 1-10, or 2-5. The molar ratio of the Group 6 metal to the Group 7-10 metal may range from 0.1-20, 1-10, or 2-5. In certain embodiments, the catalyst comprises a Group 15 element (s) in addition to the combination of Group 6 metal (s) and one or more metals from Groups 5 and / or Groups 7-10. In other embodiments, the catalyst comprises a Group 6 metal (s) and a Group 10 metal (s). Of the catalysts, the molar ratio of the total Group 10 metal to the total Group 6 metal may be in the range of 1 to 10, or 2 to 5. In certain embodiments, the catalyst comprises a Group 5 metal (s) and a Group 10 metal (s). In the catalyst, the molar ratio of the total Group 10 metal to the total Group 5 metal may be in the range of 1 to 10, or 2 to 5.

In certain embodiments, the Group 5-10 metal (s) are incorporated into or deposited on a carrier to form a catalyst. In certain embodiments, the Group 5-10 metal (s) are combined with the Group 15 element (s) to incorporate into or deposit on the carrier to form a catalyst. In embodiments in which the metal (s) and / or element (s) are supported, the weight of the catalyst includes all carriers, all metal (s), and all element (s). The carrier may be porous and may also include refractory oxides, porous carbonaceous materials, zeolites, or combinations thereof. The refractory oxide may include, but is not limited to, alumina, silica, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, or mixtures thereof. Carriers can be obtained from manufacturers such as Criterion Catalysts and Technologies LP (Houston, Texas, U.S.A.). Porous carbonaceous materials include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include Y-zeolites, beta zeolites, Mordenite zeolites, ZSM-5 zeolites, and ferrierite zeolites. Zeolites can be obtained from manufacturers such as Zelyst (Valley forge, Pennsylvania, U.S.A.).

The carrier is, in some embodiments, made such that the carrier has an average pore diameter of at least 150 mm, at least 170 mm, or at least 180 mm. In some embodiments, the carrier is made by molding an aqueous paste of the carrier material. In some embodiments, acid is added to the paste to assist in extruding the paste. Water and dilute acid are added in the amounts and methods necessary to impart the required consistency to the extrudable paste. Examples of the acid include, but are not limited to nitric acid, acetic acid, sulfuric acid, and hydrochloric acid.

To form the extrudate, the paste can be extruded and cut using known catalyst extrusion methods and catalyst cutting methods. The extrudate is subjected to a temperature in the range of 5 to 260 ° C. or 85 to 235 ° C. for a period of time (eg for 0.5 to 8 hours) and / or until the moisture content in the extrudate reaches the required level. Heat treatment at This heat treated extrudate can be further heat treated at a temperature in the range of 800-1200 ° C. or 900-1100 ° C. to form a carrier having an average pore diameter of at least 150 mm 3.

In certain embodiments, the carrier comprises gamma alumina, theta alumina, delta alumina, alpha alumina, or combinations thereof. The amount of gamma alumina, delta alumina, alpha alumina, or combinations thereof is in the range of 0.0001-0.99 grams, 0.001-0.5 grams, 0.01-0.1 grams per gram of catalyst carrier, as determined by x-ray diffraction, or Up to 0.1 grams. In certain embodiments, the carrier, alone or in combination with other forms of alumina, is 0.1-0.99 grams, 0.5-0.9 grams, or 0.6 per gram of catalyst carrier, as determined by x-ray diffraction. Have a theta alumina content in the range of ˜0.8 grams. In certain embodiments, the carrier can have at least 0.1 grams, at least 0.3 grams, at least 0.5 grams, or at least 0.8 grams of theta alumina as determined by x-ray diffraction.

Carrier catalysts can be prepared using known catalyst preparation techniques. US Patent No. 6,218,333 to Gabriele et al .; US Patent No. 6,290,841 to Gabriel Rove et al .; And examples of catalyst preparation are disclosed in U.S. Patent No. 5,744,025 to Boon et al. And U.S. Patent Application Publication No. 20030111391 for Bhan's application.

In certain embodiments, the catalyst may be impregnated with a metal to form a catalyst. In certain embodiments, the carrier is heat treated at a temperature in the range of 400-1200 ° C., 450-1000 ° C., or 600-900 ° C. prior to impregnation of the metal. In some embodiments, impregnation aids may be used during the preparation of the catalyst. Examples of impregnation aids include citric acid component, ethylenediamine tetraacetic acid (EDTA), ammonia, or mixtures thereof.

In some embodiments, the catalyst may be formed by addition or incorporation of Group 5-10 metal (s) into a mixture of heat-molded carrier (“overlayin”). Overlaying a metal on a heat-treated molded carrier having a substantially or relatively uniform metal concentration provides the catalyst with desirable catalytic properties in many cases. After each metal overlay, the heat treatment of the shaped carrier tends to improve the catalytic activity of the catalyst. Methods of preparing the catalyst using the overlay method are described in US Patent Application Publication No. 20030111391 to Bhan's application.

The Group 5-10 metal (s) and carrier can be mixed with a suitable mixing device to form the Group 5-10 metal (s) / carrier mixture. The Group 5-10 metal (s) / carrier mixture can be mixed using a suitable mixing device. Examples of suitable mixing devices include tumblers, stationary shells or troughs, muller mixers (eg, batch type or continuous type), impact mixers, and other known mixers, or 5 Well-known devices suitable for providing a Group 10 metal (s) / carrier mixture. In certain embodiments, the materials are mixed until the Group 5-10 metal (s) are substantially homogeneously dispersed in the carrier.

In certain embodiments, the catalyst is heat treated at a temperature in the range of 150-750 ° C., 200-740 ° C., or 400-730 ° C. after the carrier is combined with the metal.

In some embodiments, the catalyst may be heat treated at temperatures ranging from 400 ° C. to 1000 ° C. in the presence of hot air and / or oxygen enriched air to remove volatiles such that at least some of the Group 5-10 metals are attached thereto. Can be converted to the corresponding metal oxide.

However, in some embodiments, the catalyst is in the 35-500 ° C. range (eg, less than 300 ° C., 400 ° C.) in the atmosphere to remove most of the volatile components without conversion of the Group 5-10 metals to the metal oxides. Heat treatment at a temperature of less than or less than 500 ° C.) for 1 to 3 hours. Catalysts prepared in this way are commonly referred to as "uncalcined" catalysts. When the catalyst is prepared in this manner in combination with the sulfiding method, the active metals can be substantially dispersed in the carrier. The preparation of such catalysts is described in US Pat. No. 6,218,333 and US Pat. No. 6,290,841 to Gabriellobe et al.

In certain embodiments, the theta alumina carrier can be combined with Group 5-10 metals to form a mixture of theta alumina carrier / 5-10 metals. The mixture of theta alumina carriers Group 5-10 metals may be heat treated at a temperature of at least 400 ° C. to form a catalyst having a pore size distribution having an average pore diameter of at least 230 mm 3. Typically, this heat treatment is carried out at temperatures up to 1200 ° C.

In some embodiments, the carrier (commercially available carrier or carrier prepared as described herein) may be combined with a supported catalyst and / or bulk metal catalyst. In some embodiments, the supported catalyst can comprise Group 15 metal (s). For example, the supported catalyst and / or bulk metal catalyst may be ground to a powder having an average particle size of 1-50 microns, 2-45 microns, or 5-40 microns. This powder is combined with a carrier to form an embedded metal catalyst. In certain embodiments, the powder is combined with a carrier and then extruded using standard techniques to produce a pore size distribution having an average pore diameter in the range of 80-200 mm or 90-180 mm, or 120-130 mm. It is possible to form a catalyst having.

In some embodiments, combining the catalyst with a carrier allows at least a portion of the metal to be present below the surface of the metal supported catalyst (eg, contained within the carrier), thereby ununembedded Less metal is present on the surface than in the case of metal catalysts. In some embodiments, having less metal on the surface of the catalyst allows at least a portion of the metal to migrate to the surface of the catalyst during use, thereby extending the life and / or catalyst activity of the catalyst. The metal may migrate to the catalyst surface through erosion of the catalyst surface during contact of the catalyst with the crude oil feed.

In certain embodiments, the intercalation and / or mixing of the catalyst components results in a structured order of the Group 6 metals in the Group 6 oxide crystal structure, which in turn results in a 6 in the crystal structure of the embedded catalyst. It turns into a substantially random arrangement of group metals. The order of the Group 6 metals can be determined using powder x-ray diffraction. The arrangement of the elemental metals in the catalyst relative to the arrangement of the elemental metals in the metal oxide is determined by the x-ray diffraction spectrum of the Group 6 oxide relative to the arrangement of the Group 6 metal peaks in the catalyst's x-ray diffraction spectrum. It can be found by comparing the arrangement of the Group 6 metal peaks. From the broadening and / or absence of patterns associated with the Group 6 metal in the x-ray diffraction spectrum, it can be estimated that the Group 6 metal (s) are arranged substantially randomly in the crystal structure.

For example, molybdenum trioxide and an alumina carrier having an average pore diameter of at least 180 mm 3 can be combined to form an alumina / molybdenum trioxide mixture. Molybdenum trioxide has a constant pattern (eg, constant D ₀₀₁ , D ₀₀₂ and / or D ₀₀₃ peaks). The alumina / group 6 trioxide mixture is heat treated at a temperature of at least 538 ° C. (1000 ° F.) to produce a catalyst that does not show a pattern for molybdenum dioxide in the x-ray diffraction spectrum (eg, the absence of the D ₀₀₁ peak). can do.

In certain embodiments, the catalyst is characterized by having a pore structure. Various pore structure parameters include, but are not limited to, pore diameter, pore volume, surface area, or combinations thereof. It can have a distribution called total amount of pore size versus pore diameter. The average pore diameter of the pore size distribution can be in the range of 30-1,000 mm, 50-500 mm, or 60-300 mm. In certain embodiments, a catalyst comprising at least 0.5 grams of gamma alumina per gram of catalyst has a pore size distribution having an average pore diameter in the range of 60-200 kPa, 90-180 kPa, 100-140 kPa, or 120-130 kPa. . In other embodiments, the catalyst comprising at least 0.1 gram of theta alumina per gram of catalyst has a pore size distribution having an average pore diameter in the range of 180-500 kPa, 200-300 kPa, 230-250 kPa. In some embodiments, the average pore diameter of the pore size distribution is at least 120 mm, at least 150 mm, at least 180 mm, at least 200 mm, at least 220 mm, at least 230 mm, or at least 300 mm. These average pore diameters are typically up to 1000 mm 3.

The catalyst may have a pore size distribution having an average pore diameter of at least 60 mm 3 or at least 90 mm 3. In some embodiments, the catalyst has a pore size distribution having an average pore diameter in the range of 90-180 mm 3, 100-140 mm 3, or 120-130 mm 3, wherein at least 60% of the total number of porosities of the pore size distribution is the average pore diameter. It has a pore diameter within 45 kHz, 35 kHz, or 25 kHz. In certain embodiments, the catalyst has a pore size distribution having an average pore diameter in the range of 70-180 mm 3, wherein at least 60% of the total number of porosities in the pore size distribution is within 45 mm, 35 mm 3, or 25 mm 3 of the average pore diameter. Has a pore diameter of.

In embodiments in which the average pore diameter of the pore size distribution is at least 180 mm, at least 200 mm, or at least 230 mm, the pore diameter within 50 mm, 70 mm, or 90 mm is at least 60% of the total pore size of the pore size distribution. Has In certain embodiments, the catalyst has a pore size distribution having an average pore diameter in the range of 180-500 kPa, 200-400 kPa, or 230-300 kPa, wherein at least 60% of the total pore size of the pore size distribution is the average pore diameter. It has a pore diameter within 50 kPa, 70 kPa, or 90 kPa.

In some embodiments, the pore volume of the pores can be at least 0.3 cm ³ / g, at least 0.7 cm ³ / g or at least 0.9 cm ³ / g. In some embodiments, the void volume of the pores may be in the range of 0.3-0.99 cm ³ / g, 0.4-0.8 cm ³ / g, or 0.5-0.7 cm ³ / g.

Catalysts having a pore size distribution having an average pore diameter in the range of 90-180 mm 3, in some embodiments, may be at least 100 m ² / g, at least 120 m ² / g, at least 170 m ² / g, at least 220 m ² / g or a surface area of at least 270 m ² / g. Such surface area may be in the range of 100-300 m ² / g, 120-270 m ² / g, 130-250 m ² / g, or 170-220 m ² / g.

In certain embodiments, a catalyst having a pore size distribution having an average pore diameter in the range of 180-300 mm 3 can be at least 60 m ² / g, at least 90 m ² / g, at least 100 m ² / g, at least 120 m ² / g, or a surface area of at least 270 m ² / g. Such surface area may be in the range of ^{60 ~ 300 m 2 / g,} 90 ~ 280 m 2 / g, 100 ~ 270 m 2 / g, or 120 ~ 250 m ² / g.

In certain embodiments, the catalyst is present in the form of pellets, for example, pellets, cylinders, and / or extrudates. The catalyst usually has a plate breaking strength within the range of 50 to 500 N / cm, 60 to 400 N / cm, 100 to 350 N / cm, 200 to 300 N / cm, or 220 to 280 N / cm.

In certain embodiments, the catalyst and / or catalyst precursor are known techniques known in the art (eg, ACTICAT ^™ Process, CRI International, Inc.) to sulfide to form a metal sulfide (prior to use). In some embodiments, the catalyst can be sulfided after drying. Alternatively, the catalyst may be contacted with a crude oil feed containing a sulfur containing compound to sulfide in situ. In situ sulfidation can utilize gaseous hydrogen sulfide in the presence of hydrogen or liquid sulfiding agents such as organosulfur compounds (including alkyl sulfides, poly sulfides, thiols, and sulfoxides). Off-site sulfidation processes are described in US Pat. No. 5,468,372 and US Pat. No. 5,688,736 to Seamans et al.

In certain embodiments, the first type of catalyst ("first catalyst"), in combination with a carrier, comprises a pore size distribution comprising a Group 5-10 metal (s) and having an average pore diameter in the range of 150-250 mm 3. Have The first catalyst may have a surface area of at least 100 m ² / g. The pore volume of the first catalyst may be at least 0.5 cm ³ / g. The first catalyst has a gamma alumina content of at least 0.5 cm ³ / g and may typically have a maximum of 0.9999 grams of gamma alumina per gram of the first catalyst. The first catalyst, in some embodiments, has a total content of Group 6 metal (s) in the range of 0.0001 to 0.1 grams per gram of catalyst. The first catalyst may remove some of the Ni / V / Fe from the crude oil feed, remove some of the components that contribute to increasing the TAN of the crude feed, and C ₅ from the crude feed. At least a portion of the asphaltenes may be removed and at least some of the metals or combinations thereof in the organic acid metal salt in the crude oil feed may be removed. When the crude feed is in contact with the first catalyst, other properties (eg, sulfur content, VGO content, API specific gravity, residue content, or combinations thereof) show relatively little variation. The ability to selectively change the characteristics of the crude oil feed, with other characteristics changing only a relatively small amount, makes the crude oil feed more efficient. In some embodiments, one or more first catalysts may be used in any order.

In certain embodiments, the second type of catalyst (“second catalyst”), in combination with a carrier, comprises pore size 5-10 metal (s) and has a pore size distribution having an average pore diameter in the range of 90-180 mm 3. Has At least 60% of the total number of pores in the pore size distribution of the second catalyst has a pore diameter within 45 kPa which is an average pore diameter. Contacting the crude feed with the second catalyst under suitable contact conditions will produce a crude oil product having selected properties (e.g., TAN) that are significantly changed for the same properties of the crude feed while only minor changes are made to other properties. Can be. In some embodiments, a hydrogen source may be present during the contact.

The second catalyst can reduce at least some of the components that contribute to increasing the TAN of the crude oil feed, at least some of the components that cause the relatively high viscosity, and can also reduce at least a portion of the Ni / V / Fe content of the crude oil product. Can be reduced. In addition, contacting the crude oil feed with the second catalyst can produce crude oil products with relatively little variation in sulfur content relative to the sulfur content of the crude oil feed. For example, the crude oil product may have a sulfur content of 70% -130% of the sulfur content of the crude oil feed. Crude oil products show relatively little variation in crude oil feed in distillate content, VGO content, and residue content.

In some embodiments, the Ni / V / Fe content of the crude oil feed is relatively low (eg, up to 50 wtppm), but the content of metals in the TAN, asphaltene content, or organic acid metal salt may be relatively high. If the TAN is relatively high (eg, a TAN of at least 0.3), the crude oil feed will be unsuitable for transportation and / or refining. C ₅ asphaltene content of the oil is relatively high relative to C ₅ lower It shows lower stability during processing compared to other crude oils with low asphaltene content. Contacting the crude feed with the second catalyst can remove from the crude feed the acidic components and / or C ₅ asphaltenes that cause the TAN to rise. In certain embodiments, reducing the components responsible for raising C ₅ asphaltenes and / or TAN can reduce the viscosity of the crude feed / crude product mixture relative to the viscosity of the crude feed. In some embodiments, one or more combinations of the second catalysts, when used to treat a crude feed, as described herein, improve the stability of the final product / crude product mixture, extend catalyst life, Minimal net hydrogen uptake by the crude oil feed or combinations thereof.

In certain embodiments, a third type of catalyst ("third catalyst") can be obtained by combining a carrier with a Group 6 metal (s) to produce a catalyst precursor. The catalyst precursor is one or more sulfur containing compounds. In the presence of them can be heated at a temperature below 500 ° C. (eg, below 482 ° C.) for a relatively short time to form an unbaked third catalyst Typically, this catalyst precursor is heated at least 100 ° C. for 2 hours. In certain embodiments, the third catalyst has a Group 15 element content in the range of 0.001 to 0.03 grams, 0.005 to 0.02 grams, or 0.008 to 0.01 grams, per gram of catalyst. When used to process crude oil feeds, as shown, sufficient activity and stability In certain embodiments, the catalyst precursor is at a temperature below 500 ° C. in the presence of one or more sulfur compounds. Can be heated at

The third catalyst can remove at least some of the components that contribute to raising the TAN of the crude oil feed, can remove at least some of the metals in the organic acid metal salts, and can reduce the Ni / V / Fe content of the crude product In addition, the viscosity of the crude oil product can be lowered. In addition, contacting the crude oil feed with a third catalyst can produce crude oil products that have a relatively small variation in sulfur content relative to the sulfur content of the crude feed and also have a relatively low net hydrogen uptake by the crude feed. . For example, the crude product may have a sulfur content of 70% -130% of the sulfur content of the crude feed. In addition, crude oil products prepared using the third catalyst may show relatively small variations in API specific gravity, distillate content, VGO content, and residue content for the crude oil feed. Ability to reduce the TAN of crude oil products, metals in the form of metal salts of organic salts, Ni / V / Fe content, and viscosity while changing API specific gravity, distillate content, VGO content, and residue content in crude oil feeds in small amounts Thanks to this, the crude oil product can be used by various processing facilities.

The third catalyst, in some embodiments, may reduce at least a portion of the MCR content of the crude feed while maintaining the crude feed / final product stability. In certain embodiments, the third catalyst has a Group 6 metal (s) content in the range of 0.0001 to 0.1 grams, 0.005 to 0.05 grams, or 0.001 to 0.01 grams, and 0.0001 to 0.05 grams, 0.005 to 0.03 grams per gram of catalyst Or, group 10 metal (s) content in the range of 0.001 to 0.01 gram. Group 6 and Group 10 metal (s) catalysts are used in MCR in crude oil feed at temperatures ranging from 300 to 500 ° C. or 350 to 450 ° C. and pressures ranging from 0.1 to 10 MPa, 1 to 8 MPa, or 2 to 5 MPa. It may facilitate the reduction of at least some of the components that contribute to the content.

In certain embodiments, the fourth type of catalyst ("fourth catalyst") comprises Group 5 metal (s) in combination with the theta alumina carrier. The fourth catalyst has a pore size distribution having an average pore diameter of at least 180 mm 3. In some embodiments, the average pore diameter of the fourth catalyst can be at least 220 kPa, at least 230 kPa, at least 250 kPa, or at least 300 kPa. The carrier may comprise at least 0.1 grams, at least 0.5 grams, at least 0.8 grams, or at least 0.9 grams of theta alumina per gram of carrier. The fourth catalyst, in some embodiments, may include up to 0.1 grams of Group 5 metal (s) per gram of catalyst and at least 0.0001 grams of Group 5 metal (s) per gram of catalyst. In certain embodiments, the Group 5 metal is vanadium.

In some embodiments, the crude oil feed can be contacted with the additional catalyst following the contact with the fourth catalyst. The additional catalyst may be one or more of a first catalyst, a second catalyst, a third catalyst, a fifth catalyst, a sixth catalyst, a seventh catalyst, commercially available catalysts described herein, or a combination thereof.

In some embodiments, hydrogen may be produced while the crude oil feed is in contact with the fourth catalyst at a temperature ranging from 300-400 ° C., 320-380 ° C., or 330-370 ° C. The crude oil product produced at such a contact may have a TAN of up to 90%, up to 80%, up to 50%, or up to 10% of the TAN of the crude oil feed. Hydrogen generation may be in the range of 1-50 Nm ³ / m ³ , 10-40 Nm ³ / m ³ , or 15-25 Nm ³ / m ³ . Crude oil products may have a total Ni / V / Fe content of up to 90%, up to 80%, up to 70%, up to 50%, up to 10%, or at least 1% of the total Ni / V / Fe content of the crude oil feed. have.

In certain embodiments, the fifth type of catalyst (“fifth catalyst”) comprises a Group 6 metal (s) in combination with the theta alumina carrier. The fifth catalyst has a pore size distribution having an average pore diameter of at least 180 kPa, at least 220 kPa, at least 230 kPa, at least 250 kPa, at least 300 kPa, or at most 500 kPa. The carrier may comprise at least 0.1 grams, at least 0.5 grams, or at most 0.999 grams of theta alumina per gram of carrier. In certain embodiments, the carrier has an alpha alumina content of less than 0.1 gram of alpha alumina per gram of catalyst. The catalyst, in some embodiments, comprises up to 0.1 grams of Group 6 metal (s) per gram of catalyst and at least 0.0001 grams of Group 6 metal (s) per gram of catalyst. In certain embodiments, the Group 6 metal (s) are molybdenum and / or tungsten.

In certain embodiments, when the crude feed is contacted with the fifth catalyst at a temperature in the range 310-400 ° C., 320-370 ° C., or 330-360 ° C., the net hydrogen uptake by the crude oil feed is relatively low. (Eg, 0.01-100 Nm ³ / m ³ , 1-80 Nm ³ / m ³ , 5-50 Nm ³ / m ³ , or 10-30 Nm ³ / m ³ ). The net hydrogen uptake by the crude oil feed may, in some embodiments, be in the range 1-20 Nm ³ / m ³ , 2-15 Nm ³ / m ³ , or 3-10 Nm ³ / m ³ . The crude product produced by contacting the crude feed with the fifth catalyst may have a TAN of up to 90%, up to 80%, up to 50%, or up to 10% of the TAN of the crude feed. TAN of the crude oil product may be in the range of 0.01 to 0.1, 0.03 to 0.05, or 0.02 to 0.03.

In certain embodiments, the sixth type of catalyst ("sixth catalyst") comprises Group 5 metal (s) and Group 6 metal (s) in combination with the theta alumina carrier. The sixth catalyst has a pore size distribution having an average pore diameter of at least 180 mm 3. In some embodiments, the average pore diameter of the pore size distribution can be at least 220 mm, at least 230 mm, at least 250 mm, at least 300 mm, or at most 500 mm. The carrier may comprise at least 0.1 grams, at least 0.5 grams, at least 0.8 grams, at least 0.9 grams, or at most 0.99 grams of theta alumina per gram of carrier. In certain embodiments, the catalyst may comprise a total content of Group 5 metal (s) and Group 6 metal (s) of the catalyst, per gram of catalyst, at most 0.1 grams, at least 0.0001 grams. . In certain embodiments, the molar ratio of the Group 6 metal sum to the Group 5 metal sum may be in the range of 0.1-20, 1-10, or 2-5. In certain embodiments, the Group 5 metal is vanadium and the Group 6 metal (s) are molybdenum and / or tungsten.

Crude oil feed is in contact with the sixth catalyst 310 ~ 400 ℃, at 320 ~ 370 ℃, or the temperature of 330 ~ 360 ℃ range, the net hydrogen uptake by the crude feed was -10 Nm ³ / m ³ ~ 20 Nm ³ / m ³ , -7 Nm ³ / m ³ to 10 Nm ³ / m ³ , or -5 Nm ³ / m ³ to 5 Nm ³ / m ³ range. Negative net hydrogen uptake is one indicator that hydrogen is being produced in situ. The crude product produced by contacting the crude feed with the sixth catalyst has a TAN of at most 90%, at most 80%, at most 50%, at most 10%, or at least 1% of the TAN of the crude feed. The TAN of the crude oil product may be in the range of 0.01 to 0.1, 0.02 to 0.05, or 0.03 to 0.04.

Low net hydrogen uptake while the crude feed is in contact with the fourth, fifth, or sixth catalyst lowers the total demand for hydrogen during the treatment process while producing a crude oil product suitable for transfer and / or treatment. Since the production of hydrogen and / or the transfer of hydrogen is costly, minimizing the use of hydrogen in any process reduces the overall process cost.

In certain embodiments, the seventh type of catalyst (“seventh catalyst”) has a total content of Group 6 metal (s) in the range of 0.0001 to 0.06 grams per gram of catalyst. Group 6 metals comprise molybdenum and / or Or tungsten The seventh catalyst helps to produce crude oil products having a TAN of up to 90% of the TAN of the crude oil feed.

Other embodiments of the first, second, third, fourth, fifth, sixth, and seventh catalysts may be constructed and / or used differently than described herein.

By selecting the catalyst (s) of the present application and controlling the operating conditions, it is possible to produce crude oil products with altered TAN and / or select properties for the crude oil feed without significantly altering other characteristics of the crude oil feed. have. The resulting crude oil product may have improved properties than the crude oil feed, and thus may be more suitable for conveying and / or refining.

Arranging two or more catalysts in a predetermined order may control the order of improving properties for the crude oil feed. For example, TAN of the crude oil feed, API specific gravity, at least some of the C ₅ Aspartene, at least some iron, at least some nickel, and / or at least some vanadium can be reduced before at least some heteroatoms in the crude feed are reduced.

The arrangement and / or selection of the catalyst may, in some embodiments, improve catalyst life and / or stability of the crude oil feed / final product mixture. If the catalyst life and / or stability of the crude oil feed / final product mixture is improved during the treatment process, the contact system may be operated for at least 3 months, at least 6 months, or at least 1 year without replacement of the catalyst in the contacting zone.

If the selected catalysts are combined, while maintaining the stability of the crude oil feed / final product mixture during the treatment process (e.g., maintaining crude oil feed P-value above 1.5), before the other properties of the crude oil feed are changed. At least some Ni / V / Fe, at least some C ₅ from the crude oil feed Asphaltenes, metals in at least some of the organic acid metal salts, at least some, at least some residues, or combinations thereof, that are responsible for raising the TAN can be reduced. Alternatively, by contacting the crude oil feed with the selected catalyst, C ₅ It is possible to incrementally reduce the asphaltenes, TAN and / or API specific gravity. The ability to incrementally and / or selectively change the properties of the crude oil feed allows the stability of the crude oil feed / final product mixture to be maintained during the processing.

In some embodiments, the first catalyst (described above) can be disposed upstream of the series of catalysts. This placement of the first catalyst may remove high molecular weight contaminants, metal impurities, and / or metals in the organic acid metal salt while maintaining the stability of the crude oil feed / final product mixture.

The first catalyst may, in some embodiments, remove from the crude oil feed at least some of the Ni / V / Fe, acidic components, components that cause other catalyst life reductions in the system, or combinations thereof. Can be. For example, reducing at least a portion of the C ₅ asphaltenes in the crude oil feed / final product mixture relative to the crude oil feed prevents plugging of other catalysts disposed downstream, thereby providing a contact system without replenishment of the catalyst. Extend the time it can be operated. Removing at least a portion of Ni / V / Fe from the crude oil feed may, in some embodiments, extend the life of one or more catalysts disposed after the first catalyst.

The second catalyst (s) and / or third catalyst (s) may be disposed downstream of the first catalyst. Further contact of the crude oil feed / final product mixture with the second catalyst (s) and / or third catalyst (s) results in a metal in the TAN, Ni / V / Fe content, sulfur content, oxygen content, and / or organic acid metal salt. The content can be further reduced.

In some embodiments, contacting the crude feed with the second catalyst (s) and / or third catalyst (s) maintains the stability of the crude feed / final product mixture during the processing, while maintaining the stability of the crude feed For each property, crude oil feed / final product with reduced TAN, reduced sulfur content, reduced oxygen content, reduced metal content in organic acid metal salts, reduced asphaltene content, reduced viscosity, or combinations thereof Mixtures can be prepared. The second catalyst may be arranged in series with the second catalyst upstream of the third catalyst or vice versa.

The ability to deliver hydrogen to a defined contact area helps to minimize hydrogen use during contact. Combinations of catalysts that promote the production of hydrogen during contact, and catalysts that absorb relatively small amounts of hydrogen during contact, can be used to alter the selective properties of the crude product for the same properties of the crude oil feed. For example, the fourth catalyst may be used to modify the first catalyst (s) to change other properties of the crude oil feed by only a selective amount, and / or to alter the selective properties of the crude feed while maintaining the crude feed / final product stability. ), Second catalyst (s), third catalyst (s), fifth catalyst (s), sixth catalyst (s), and / or seventh catalyst (s). The order and / or number of catalysts is selected to minimize net hydrogen uptake while maintaining crude oil feed / final product stability. Minimal net hydrogen uptake results in a residue content, VGO content, distillate content, API specific gravity of the crude oil feed, while allowing the TAN and / or viscosity of the crude oil product to be up to 90% of the TAN and / or viscosity of the crude oil feed, or Combinations of these are maintained within 20% of each characteristic of the crude feed.

If the net hydrogen uptake by the crude oil feed is reduced, a crude oil product having a boiling range distribution similar to the boiling point distribution of that crude feed, and a reduced TAN compared to the TAN of the crude feed, can be produced. In addition, the atomic H / C of the crude oil product can only be changed in relatively small amounts compared to the atomic H / C of the crude oil feed.

The generation of hydrogen in defined contact areas enables the selective addition of hydrogen to other contact areas and / or the selective reduction of the properties of the crude oil feed. In some embodiments, the fourth catalyst (s) can be disposed upstream, downstream or between additional catalyst (s) described herein. Hydrogen may be produced during contact between the crude oil feed and the fourth catalyst (s), and hydrogen is directed to the contacting zones containing the additional catalyst (s). Such delivery of hydrogen may oppose the flow of the crude oil feed. In some embodiments, the delivery of hydrogen may be cocurrent to the flow of crude oil feed.

For example, in one stacked configuration (eg, see FIG. 2B), hydrogen may be generated during contact in one contact area (eg, contact area 102 of FIG. 2B) and Hydrogen may be delivered to additional contacting regions (eg, contacting region 114 of FIG. 2B) in a direction opposite to the flow of crude oil feed. In certain embodiments, the hydrogen flow can be co-current with the flow of the crude oil feed. Alternatively, in one lamination configuration (eg, see FIG. 3B), hydrogen may be generated during contact in one contact area (eg, contact area 102 of FIG. 3B). The hydrogen source is led to the first additional contacting region in a direction opposite to the flow of crude oil feed (eg, through the conduit 106 'to add hydrogen to the contacting region 114 of FIG. 3B). ), Leading to a second additional contacting zone in a co-current manner with the flow of crude oil feed (eg, adding hydrogen to the contacting zone 116 of FIG. 3B via conduit 106 ').

In some embodiments, the fourth catalyst and the sixth catalyst are used in series with the fourth catalyst lying upstream of the sixth catalyst or vice versa. Combining the fourth catalyst with the additional catalyst (s) can reduce the TAN, Ni / V / Fe content, and / or the content of metals in the organic acid metal salt, with low net uptake of hydrogen by the crude oil feed. have. Low net hydrogen uptake may allow other properties of the crude product to be changed only in small amounts for the same properties of the crude oil feed.

In some embodiments, two different seventh catalysts may be used in combination. The seventh catalyst used upstream from the downstream seventh catalyst may have a total content of Group 6 metal (s) in the range of 0.0001 to 0.06 grams per gram of catalyst. The downstream seventh catalyst per gram of the downstream seventh catalyst. It may have a total content of Group 6 metal (s) above the total content of Group 6 metal (s) in the upstream seventh catalyst, or may have at least 0.02 grams of Group 6 metal (s) per gram of catalyst. . In some embodiments, the positions of the upstream seventh catalyst and the downstream seventh catalyst may be reversed. In the downstream seventh catalyst, the ability to use a relatively small amount of catalytically active metal allows other properties of the crude product to be changed only in small amounts for the same properties of the crude oil feed (e.g., heteroatomic content). , Relatively small variations in API specific gravity, residue content, VGO content, or combinations thereof)

Contacting the crude oil feed with the seventh catalyst upstream and downstream can produce a crude oil product having a TAN of up to 90%, up to 80%, up to 50%, up to 10%, or at least 1% of the TAN of the crude feed. have. In some embodiments, the TAN of the crude oil feed may be incrementally reduced by contacting the upstream and downstream seventh catalyst (eg, by contacting the crude oil feed with the catalyst to provide characteristics for the crude oil feed). Forming an initial crude oil product which is then contacted with an additional catalyst to produce a crude oil product whose properties have been changed for this initial crude oil product). The ability to incrementally reduce TAN helps to maintain stability of the crude oil feed / final product mixture during processing.

In some embodiments, combining catalyst selection and / or order of the catalyst with controlled contact conditions (eg, temperature and / or crude oil feed flow rate) reduces the hydrogen uptake by the crude oil feed, It is helpful to maintain the stability of the crude oil feed / final product mixture during processing and also to change one or more characteristics of the crude oil product for each of the characteristics of the crude oil feed. The stability of the crude oil feed / final product mixture can be affected by various phase separations from the crude oil feed / final product mixture. For example, insolubility of the crude oil feed and / or crude oil product, flocculation of asphaltenes from the crude oil feed / final product mixture, precipitation of components from the crude oil feed / final product mixture, or combinations thereof Due to this, phase separation may occur in the crude oil feed / final product mixture.

At some point during the contact period, the concentration of the crude feed and / or final product in the crude feed / final product mixture may vary. As the concentration of the total product in the crude oil feed / final product mixture is changed by the formation of the crude oil product, the solubility of the components of the crude oil feed / final product mixture and / or the solubility of the components of the final product is changed. . For example, the crude feed may contain components that can be dissolved in the crude feed at the start of the processing process. As properties of the crude oil feed (eg, TAN, MCR, C ₅ asphaltene, P-value, or combinations thereof) change, the components may be less soluble in the crude feed / final product mixture. do. In some cases, the crude oil feed and the final product cannot form two phases and / or dissolve each other. Variation in solubility also results in the crude oil feed / final product mixture forming two or more phases. Formation of two phases through the aggregation of asphaltenes results in variations in the concentration of the crude oil feed and in the final product, and / or precipitation of components shortens the life of one or more catalysts. In addition, the efficiency of the treatment process may be reduced. For example, repeated processing of the crude oil feed / final product mixture may be necessary to produce crude oil products with the desired properties.

During the treatment process, the P-value of the crude oil feed / final product mixture can be monitored and the stability of the crude oil feed / final product mixture can be estimated. Typically, a P-value of up to 1.5 indicates that aggregation of asphaltenes from crude oil feed generally occurs. If the P-value is initially at least 1.5, this P-value is increased or relatively stable during contact, which indicates that the crude feed is relatively stable during contact. By controlling the contact conditions, by selecting the catalyst, it is possible to control the crude oil feed / final product mixture stability calculated by the P-value, either by selective order of the catalyst or by a combination thereof. Control of such contact conditions may include LHSV, temperature, pressure, hydrogen uptake, crude oil feed flow, or a combination thereof.

In some embodiments, the contact temperatures are controlled to remove C ₅ asphaltenes and / or other asphaltenes while maintaining the MCR content of the crude oil feed. Reduction of MCR content through hydrogen absorption and / or higher contact temperatures may result in the formation of a biphasic phase that may reduce the stability of the crude oil feed / final product mixture and / or the lifetime of one or more catalysts. When combining the control of contact temperatures and hydrogen uptake with the catalyst described herein, the C ₅ content of the crude oil feed can be changed in a relatively small amount It is possible to reduce the asphaltene content.

In some embodiments, the contact conditions are controlled such that temperatures in one or more contact regions are different from each other. Operating at different temperatures allows for selective variation in the crude feed characteristics while maintaining the stability of the crude feed / final product mixture. The crude oil feed enters the first contacting zone at the start of the treatment process. The first contact temperature is the temperature in the first contact region. Other contact temperatures (eg, second temperature, third temperature, fourth temperature, etc.) are temperatures in the contact region disposed behind the first contact region. The first contact temperature may be in the range of 100-420 ° C., and the second contact temperature may be in the range of 20-100 ° C., 30-90 ° C., or 40-60 ° C., different from the first contact temperature. In some embodiments, the second contact temperature is higher than the first contact temperature. With different contact temperatures, the TAN and / or C _{5 of the} crude oil feed may be to a greater extent than if the first and second contact temperatures, which may be the same, or had a temperature difference within 10 ° C of each other. TAN and / or C ₅ of crude oil products relative to asphaltene content It is possible to reduce the asphaltene content.

For example, the first contacting region may comprise the first catalyst (s) and / or the fourth catalyst (s), and the second contacting region may comprise the other catalyst (s) described herein. . The first contact temperature may be 350 ° C, and the second contact temperature may be 300 ° C. When the crude oil feed is contacted at a higher temperature with the first catalyst and / or the fourth catalyst in the first contacting zone, before contacting the other catalyst (s) in the second contacting zone, first and second in the case the difference between the contact temperature is less than 10 ℃, the same oil feed TAN and / or C ₅ asphaltene reduction in greater crude feed TAN and / or compared with C ₅ Asphaltene reduction can be obtained.

Example

     The following describes embodiments of a system having a carrier preparation, a catalyst preparation, and a selected arrangement of catalysts and controlled contact conditions, but is not limited to these examples.

Example  1. Catalyst Carrier  Produce

576 grams of alumina (Criterion Catalyst and Technologies Elp, Michigan City, Michigan, USA, with 585 grams of water and 8 grams of glacial nitric acid) , USA)) was ground for 35 minutes to prepare a carrier. The resulting powdered mixture was transferred to 1.3 Trilobe ^™. The resultant was extruded through a die plate, dried at a temperature of 90 ° C to 125 ° C, and calcined at 918 ° C to obtain a 650 gram calcined carrier having an average pore diameter of 182 mm 3. This calcined carrier was placed in a Lindberg furnace. The temperature of this furnace was raised to 1000-1100 degreeC over 1.5 hours, and it hold | maintained for 2 hours in this temperature range, and the carrier was manufactured. When determined by x-ray diffraction, this carrier contained 0.0003 grams of gamma alumina, 0.0008 grams of alpha alumina, 0.0208 grams of delta alumina, and 0.9781 grams of theta alumina per gram of carrier. This carrier had a surface area of 110 m ² / g and a total pore volume of 0.821 cm ³ / g. This carrier had a pore size distribution having an average pore diameter of 232 mm 3, and 66.7% of the total pore number of this pore size distribution had a pore diameter within an average pore diameter of 85 mm 3.

This example shows a process for preparing a carrier having a pore size distribution of at least 180 mm 3 and containing at least 0.1 gram of theta alumina.

Example  2. Average air gap of at least 230Å Diameter  Preparation of Vanadium Catalysts with Pore Size Distributions Having.

A vanadium catalyst was prepared by the following method. A vanadium impregnated solution prepared by combining 7.69 grams of VOSO ₄ and 82 grams of deionized water was impregnated with the alumina carrier prepared by the method described in Example 1. The pH of the solution was 2.27.

The alumina carrier (100 g) was impregnated in the vanadium impregnated solution, sometimes agitated and aged for 2 hours, dried at 125 ° C. for several hours, and then calcined at 480 ° C. for 2 hours. The resulting catalyst comprised 0.04 grams of vanadium per gram of catalyst and the carrier as the remainder. The vanadium catalyst had a pore size distribution with an average pore diameter of 350 mm ³ , a pore volume of 0.69 cm ³ / g, and a surface area of 110 m ² / g. In addition, 66.7% of the total number of pores in the pore size distribution of the vanadium catalyst had a pore diameter within an average pore diameter of 70 mm 3.

This example shows the preparation of a Group 5 catalyst with a pore size distribution having an average pore diameter of at least 230 mm 3.

Example  3. Average air gap of at least 230Å Diameter  Preparation of Molybdenum Catalyst with Pore Size Distribution Having.

The molybdenum catalyst was prepared by the following method. The alumina carrier prepared by the method described in Example 1 was impregnated into the molybdenum impregnation solution. The molybdenum impregnation solution is 4.26 grams of (NH ₄ ) ₂ Mo ₂ O ₇ , 6.38 grams of MoO ₃ , 1.12 grams of 30% H ₂ O ₂ , 0.27 grams of monoethanolamine (MEA), and 6.51 grams of deionization Prepared by combining water to form a slurry. The slurry was heated to 65 ° C. until the solids dissolved. The heated solution was cooled to room temperature. The pH of the solution was 5.36. With deionized water, the volume of the solution was adjusted to 82 mL.

An alumina carrier (100 grams) was impregnated into the molybdenum impregnation solution, aged with stirring occasionally for 2 hours, dried at 125 ° C. for several hours, and then calcined at 480 ° C. for 2 hours. The resulting catalyst contained 0.04 grams of molybdenum per gram of catalyst and the remainder of the carrier. The molybdenum catalyst had a pore size distribution with an average pore diameter of 250 mm ³ , a pore volume of 0.77 cm ³ / g, and a surface area of 116 m ² / g. In addition, in the pore size distribution of this molybdenum catalyst, 67.7% of the total number of pores had a pore diameter within an average pore diameter of 86 mm 3.

This example shows the preparation of a Group 6 metal catalyst having a pore size distribution having an average pore diameter of at least 230 mm 3.

Example  4. Average air gap of at least 230Å Diameter  Preparation of Molybdenum / Vanadium Catalysts with Pore Size Distributions Having.

A molybdenum / vanadium catalyst was prepared by the following method. An alumina carrier prepared by the method described in Example 1 was impregnated into a molybdenum / vanadium impregnation solution made as follows. 2.14 grams of (NH ₄ ) ₂ Mo ₂ O ₇ , 3.21 grams of MoO ₃ , 0.56 grams of 30% hydrogen peroxide (H ₂ O ₂ ), 0.14 grams of monoethanolamine (MEA), and 3.28 grams of deionized water The first solution was prepared by mixing to form a slurry. The slurry was heated to 65 ° C. until the solids dissolved. This heated solution was cooled to room temperature.

3.57 grams of VOSO ₄ and 40 grams of deionized water were combined to prepare a second solution. The first solution and the second solution were combined and sufficient deionized water was added to make the combined solution volume 82 mL to prepare a molybdenum / vanadium impregnated solution. Alumina was impregnated in this molybdenum / vanadium impregnated solution, aged for two hours with occasional stirring, dried at 125 ° C. for several hours, and then calcined at 480 ° C. for two hours. The resulting catalyst was obtained per gram of catalyst. 0.02 grams of vanadium and 0.02 grams of molybdenum and the rest were included. This molybdenum / vanadium catalyst had a pore size distribution with an average pore diameter of 300 mm 3.

This example shows the preparation of Group 5 metals and Group 6 metal catalysts having a pore size distribution having an average pore diameter of at least 230 mm 3.

Example  5. Crude Oil Feed  Contact with three catalysts.

The tubular reactor with a central batch of thermal wells was equipped with a thermocouple measuring the temperature across the catalyst bed. The catalyst bed was formed by filling the space between the heat well and the inner wall of the reactor with catalyst and silicon carbide (20-grid, Stanford Materials; Aliso Viez, CA). Such silicon carbide is believed to have low catalytic properties, even at the expense of the process described herein. All catalysts were combined with the same volume of silicon carbide before placing the mixture in the contacting zone of the reactor.

The crude oil feed flow to the reactor was from the top of the reactor to the bottom of the reactor. Silicon carbide was placed at the bottom of the reactor and served as the bottom carrier. A bottom catalyst / silicon carbide mixture (42 cm ³ ) was placed on top of the silicon carbide to form a bottom contact region. This lower catalyst had a pore size distribution with a 77 mm average pore diameter, with 66.7% of the total number of pores in this pore size distribution having a pore diameter within 20 mm average pore diameter. The bottom catalyst contained 0.095 grams of molybdenum and 0.025 grams of nickel per gram of catalyst and the remainder of the alumina carrier.

A central catalyst / silicon carbide mixture (56 cm ³ ) was placed above the lower contact area to form a central contact area. This central catalyst had a pore size distribution with an average pore diameter of 98 mm 3, and 66.7% of the total number of pores in the pore size distribution had a pore diameter within 24 mm average pore diameter. This central catalyst contained 0.02 grams of nickel and 0.08 grams of molybdenum and the remainder of the alumina carrier per gram of catalyst.

A top catalyst / silicon carbide mixture (42 cm ³ ) was placed on top of the central contact area to form the top contact area. This top catalyst had a pore size distribution with an average pore diameter of 192 mm 3, with 0.04 grams of molybdenum per gram of catalyst and the remainder mainly comprising gamma alumina carriers.

Silicon carbide was disposed on the upper contact region to fill the dead space and serve as a preheating region. The catalyst bed was mounted in a Lindbergh furnace comprising the preheating zone, the top, center, bottom contact zone, and five heating zones corresponding to the bottom carrier.

The catalysts were sulfided by introducing a gaseous mixture of 5% by volume hydrogen sulfide and 95% by volume hydrogen gas in the contact zones at a rate of 1.5 liters of gaseous mixture per total catalyst volume (mL). (Silicone carbide was not calculated as part of the volume of the catalyst.) The temperature of the contacting zones was raised to 204 ° C. (400 ° F.) over 1 hour and held at 204 ° C. for 2 hours. After maintaining at 204 ° C., the temperature of the contact areas was raised incrementally at a rate of 10 ° C. per hour up to 316 ° C. (600 ° F.). The contact areas were held at 316 ° C. for one hour, then incrementally raised to 370 ° C. (700 ° F.) over one hour and held at 370 ° C. for two hours. The contact areas were cooled to room temperature.

The crude oil feed from the Mars platform in the Gulf of Mexico was purified and then heated in an oven at a temperature of 93 ° C. (200 ° F.) for 12-24 hours to produce a crude oil feed having the characteristics set forth in Table 1 of FIG. 7. Formed. This crude feed was fed to the top of the reactor. This crude feed flowed through the preheating zone, the top contact zone, the central contact zone, the bottom contact zone, and the bottom carrier of the reactor. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions were as follows: the ratio of hydrogen gas to crude oil feed to the reactor was 328 Nm ³ / m ³ (2000 SCFB), LHSV 1h ⁻¹ , and pressure 6.9 MPa (1014.7 psi). The three contact zones were heated to 370 ° C. (700 ° F.) and held at 370 ° C. for 500 hours. The temperatures in the three contact zones then rose and were maintained in the following order: 379 ° C. (715 ° F.) 500 hours, then 388 ° C. (730 ° F.) 500 hours, and then 390 ° C. (734 ° F.) 1800 hours. And then 2400 hours at 394 ° C (742 ° F).

The final product (ie crude oil product and gas) exited the catalyst bed. This final product was introduced into a gas-liquid separator. In this gas phase-liquid separator, the final product was separated into crude product and gas. Gas input to the system was measured with a mass flow controller. The gas exiting the system was measured by a wet test meter. The crude product was analyzed periodically to determine the parts by weight of its components. The results listed are the average of the obtained weight percentages of the components. In Table 1 of Figure 7, the properties of the crude oil products are listed.

As shown in Table 1, of the crude oil product, per gram crude oil product, the sulfur content was 0.0075 grams, the residue content was 0.255 grams, and the oxygen content was 0.007 grams. The ratio of MCR content to C ₅ asphaltene content of the crude product was 1.9, and the total acid value was 0.09. The sum of nickel and vanadium was 22.4 wtppm.

The lifetime of the catalyst was determined by measuring the moving length versus weight of the crude oil feed by weighted average bed temperature ("WABT"). The lifetime of the catalyst can be correlated with the temperature of the catalyst bed. As the catalyst life is shortened, WABT is thought to increase. FIG. 8 is a graph showing WABT versus time (“t”) for improving crude oil feed in the contacting zone described in this example. Plot 136 is a plot showing the average WABT of these three contact zones versus the run time of contacting the top, center, bottom catalyst and crude oil feed. Over most of the trial time, the WABT of the contact area only changed by about 20 ° C. From the relatively stable WABT, it was possible to infer that the catalytic activity of the catalyst was not affected. Typically, pilot unit implementation times of 3,000 to 3,500 hours are associated with one year of commercial practice.

This embodiment provides a crude oil feed, under controlled contact conditions, with one catalyst having a pore size distribution having an average pore diameter of at least 180 mm 3, and a pore total number of pore size distributions with an average pore diameter in the range of 90-180 mm 3. It has been shown that at least 60% of the contact with further catalysts having a pore size distribution having a pore diameter within the mean pore diameter of 45 mm 3 produces a final product comprising crude oil product. As the P-value is pointed out, the crude oil feed / final product mixture stability is maintained. The crude oil product had reduced TAN, Ni / V / Fe content, sulfur content, and oxygen content as compared to the crude oil feed. The residue content and VGO content of the crude oil product were 90-110 of the same characteristics of the crude oil feed. Became%.

Example  6. 90 ~ 180Å Within range  Average void Diameter  Catalyst and crude oil feed with pore size distribution of  contact.

The reactor apparatus (excluding the number and volume of contacting zones), the catalytic sulfiding method, the final product separation method and the method of analyzing this final product were as described in Example 5. Each catalyst was mixed with the same volume of silicon carbide.

The crude oil feed flow into the reactor was from the top to the bottom of the reactor. The reactor was filled in the following manner from bottom to top. Silicon carbide was placed at the bottom of the reactor to serve as the bottom carrier. A lower catalyst / silicon carbide mixture (80 cm ³ ) was placed on top of the silicon carbide to form a bottom contact region. The bottom catalyst had a pore size distribution having an average pore diameter of 127 mm 3, and 66.7% of the total number of porosities in the pore size distribution had a pore diameter within an average pore diameter of 32 mm 3. The bottom catalyst contained 0.11 gram of molybdenum and 0.02 grams of nickel per gram of catalyst and the rest of the carrier.

An upper catalyst / silicon carbide mixture (80 cm ³ ) was placed on top of the lower contact region to form an upper contact region. The top catalyst had a pore size distribution with an average pore diameter of 100 mm 3, and 66.7% of the total number of porosities in the pore size distribution had a pore diameter within an average pore diameter of 20 mm 3. The top catalyst comprised 0.03 grams of nickel and 0.12 grams of molybdenum, and the remainder alumina per gram of catalyst. Silicon carbide was placed over the first contact region to fill a dead space to act as a preheating region. The catalyst bed was mounted in a Lindberg furnace comprising the preheating zone, the two contacting zones, and four heating zones corresponding to the lower carrier.

BS-4 crude oil (Venezuela) with the characteristics summarized in Table 2 of FIG. 9 was fed to the top of the reactor. This crude feed flowed through the preheating zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. This crude feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions were as follows: the ratio of hydrogen gas to crude oil feed provided to the reactor was 160 Nm ³ / m ³ (1000 SCFB), LHSV 1h ⁻¹ , and pressure 6.9 MPa (1014.7 psi). The two contact zones were heated to 260 ° C. (500 ° F.) and held at 260 ° C. (500 ° F.) for 287 hours. The temperature of the two contact zones was raised and maintained in the following order: For total run time 1173 hours, 190 hours at 270 ° C. (525 ° F.), 216 hours at 288 ° C. (550 ° F.), and then 360 hours at 315 ° C. (600 ° F.) and then 120 hours at 343 ° C. (650 ° F.).

The final product was discharged from the reactor and separated as described in Example 5. During the treatment process, the average TAN of the crude oil product was 0.42 and the average API specific gravity was 12.5. The crude product had 0.0023 grams of sulfur, 0.0034 grams of oxygen, 0.441 grams of VGO, and 0.378 grams of residue, per gram of crude oil product. In Table 2 of FIG. 9, other properties of the crude oil product are described.

This example contacts a crude oil feed with a catalyst having a pore size distribution having an average pore diameter in the range of 90-180 mm 3, and the residue content and VGO content of the crude product are 99% of each characteristic of the crude feed and While 100%, it shows the production of crude oil products with reduced TAN, reduced Ni / V / Fe content, and reduced oxygen content relative to the properties of the crude feed.

Example  7. Two catalysts and crude oil feed of  contact.

Reactor apparatus (excluding the number and volume of contacting zones), catalyst, final product separation method, crude oil product analysis, and catalytic sulfiding methods were the same as described in Example 6.

A crude oil feed (BC-10 crude oil) with the characteristics summarized in Table 3 of FIG. 10 was fed to the top of the reactor. Crude feed was flowed through the preheating zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. The contact conditions were as follows: the ratio of hydrogen gas to crude oil feed to the reactor was 80 Nm ³ / m ³ (500 SCFB), LHSV 2h ⁻¹ , and pressure 6.9 MPa (1014.7 psi). Both contact zones were heated incrementally to 343 ° C. (650 ° F.). The total run time was 1007 hours.

During the treatment process, the average TAN of the crude oil product was 0.16 and the average API specific gravity was 16.2. The crude product had 1.9 wtppm calcium, 6 wtppm sodium, 0.6 wtppm zinc, and 3 wtppm potassium. The crude product had 0.0033 grams of sulfur, 0.002 grams of oxygen, 0.376 grams of VGO, and 0.401 grams of residue per gram of crude oil product. Other properties of the crude oil product are listed in Table 3 of FIG.

This example contacts a crude feed with selected catalysts having a pore size distribution in the range of 90-180 mm 3, and the sulfur content, VGO content, and residue content of the crude product are 76%, 94 %, And 103%, showing crude oil products having reduced TAN, reduced total calcium, sodium, zinc, and potassium content.

Example  8-11. Four catalyst systems and crude oil feed at various contact conditions of  contact.

Each reaction apparatus (excluding the number and volume of contacting zones), each catalytic sulfidation method, each final product separation method, and each crude oil product analysis were the same as described in Example 5. All catalysts are mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst, unless otherwise indicated. The crude oil feed flowed from the top of each reactor to the bottom of the reactor. Silicon carbide was placed at the bottom of each reactor to serve as the bottom carrier. Each reactor had a lower contact area and an upper contact area. After placing the catalyst / silicon carbide mixtures in the contacting zones of each reactor, silicon carbide was placed over the top contacting zone to fill the dead space and serve as a preheating zone in each reactor. Each reactor was mounted in a Lindberg furnace containing a preheating zone, two contacting zones, and four heating zones corresponding to the lower carrier.

In Example 8, an uncalcined molybdenum / nickel catalyst / silicon carbide mixture (48 cm ³ ) was placed in the bottom contact area. The catalyst contained 0.146 grams of molybdenum, 0.047 grams of nickel, and 0.021 grams of phosphorus per gram of catalyst and the remainder of the alumina carrier.

A molybdenum catalyst / silicon carbide mixture (12 cm ³ ) was placed in the upper contact region with a catalyst having a pore size distribution with an average pore diameter of 180 mm ³ . The molybdenum catalyst had a total content of molybdenum of 0.04 grams per gram of catalyst and the balance included a carrier comprising at least 0.50 grams of gamma alumina per gram of carrier.

In Example 9, the unbaked molybdenum / cobalt catalyst / silicon carbide mixture (48 cm ³ ) was placed in both contact regions. The unbaked molybdenum / cobalt catalyst included 0.143 grams of molybdenum, 0.043 grams of cobalt, and 0.021 grams of phosphorus, and the other alumina carrier.

The molybdenum catalyst / silicon carbide mixture (12 cm ³ ) was placed in the upper contact area. The molybdenum catalyst was the same as in the top contacting zone of Example 8.

In Example 10, as described in the upper contact region of Example 8, the molybdenum catalyst was mixed with silicon carbide and placed in both contact regions (60 cm ³ ).

In Example 11, the unbaked molybdenum / nickel catalyst / silicon carbide mixture (48 cm ³ ) was placed in the bottom contact area. The unbaked molybdenum / nickel catalyst included 0.09 grams of molybdenum, 0.025 grams of nickel, and 0.01 grams of phosphorus, and the remainder of the alumina carrier, per gram of catalyst.

The molybdenum catalyst / silicon carbide mixture (12 cm ³ ) was placed in the upper contact area. This molybdenum catalyst was the same as in the upper contact region of Example 8.

Example 8 having the characteristics summarized in Table 4 of FIG. 11 by filtering crude oil from the Mars platform (Mexico only) and then heating in an oven at a temperature of 93 ° C. (200 ° F.) for 12-24 hours. A crude oil feed for ˜11 was formed. In these examples, this crude feed was fed to the top of the reactor. The crude oil feed flowed through the preheating zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. This crude feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions for each example were as follows: The ratio of hydrogen gas to crude oil feed during contact was 160 Nm ³ / m ³ (1000 SCFB), and the total pressure of each system was 6.9 MPa (1014.7 psi). This was. LHSV is was 2.0h ^-1 during the first 200 hours of contact, while the remaining contact time 1.0 h ^- has been reduced to ^one. The temperature at all contacting zones was 343 ° C. (650 ° F.) for 500 hours of contact time. After 500 hours, the temperature in all contacting zones was controlled as follows: For a total of 2300 hours of contact time, the temperature in the contacting zone was raised to 354 ° C (670 ° F) and held at 354 ° C for 200 hours. Then elevated to 366 ° C. (690 ° F.), held at 366 ° C. (690 ° F.) for 200 hours, then raised to 371 ° C. (700 ° F.), held at 371 ° C. for 1000 hours, and maintained at 385 ° C. (725 ° F.). After raising and holding at 385 ° C. for 200 hours, the final temperature was raised to 399 ° C. (750 ° F.) and held at 399 ° C. for 200 hours.

The crude oil product was analyzed periodically to determine TAN, hydrogen uptake by crude oil feed, P-value, VGO content, residue content, and oxygen content. Mean values for the properties of the crude oil products obtained in Examples 8-11 are shown in Table 5 of FIG.

FIG. 12 is a graph showing the P-value of crude product (“P”) versus run time (“t”) for each catalyst system of Examples 8-11. The crude oil feed has a P-value of at least 1.5. Plots 140, 142, 144, and 146 each represent the P-value of the crude oil product obtained by contacting the crude oil feed with the four catalyst systems of Examples 8-11. The P-value of the crude oil product for the catalyst systems of Examples 8-10 was maintained at a minimum of 1.5 for 2300 hours. In Example 11, the P-value was 1.5 or more in most of the trial time. At the end of the run for Example 11 (2300 hours), its P-value was 1.4. From the P-value of the crude product in each test, it can be inferred that the crude feed in each run remained relatively stable during contact (eg, no phase separation of the crude feed). As shown in FIG. 12, the P-value of the crude oil product remained relatively constant during a significant portion of each test, except for Example 10 where the P-value was increased.

FIG. 13 is a graph of net hydrogen uptake (“H ₂ ”) versus run time (“t”) by crude oil feed in four catalyst systems in the presence of hydrogen gas. Plots 148, 150, 152 and 154 each represent the net hydrogen uptake obtained by contacting the crude oil feed with the respective catalyst systems of Examples 8-11. The net hydrogen uptake by crude oil feed over the 2300 hour run period was in the range of 7-48 Nm ³ / m ³ (43.8-300 SCFB). As shown in FIG. 13, the net hydrogen uptake of the crude oil feed was relatively constant during each test.

FIG. 14 is a graph of residue content (“R”) versus time (“t”) of crude oil products, expressed in weight percent, for each catalyst system of Examples 8-11. In each of the four tests, the crude product had a residue content of 88-90% of the residue content of the crude feed. Plots 156, 158, 160, 162 each show the residue content of the crude oil product obtained by contacting the crude oil feed with the catalyst system of Examples 8-11. As shown in FIG. 14, the residue content of the crude oil product remained relatively constant for a significant portion of each test.

FIG. 15 is a graph of variation in API specific gravity (“ΔAPI”) versus execution time (“t”) of crude oil products in each of the catalyst systems of Examples 8-11. Plots 164, 166, 168 and 170 each represent the API specific gravity of the crude oil product obtained by contacting the crude oil feed with the catalyst system of Examples 8-11. For each of the four tests, each crude oil product was 58.3-72.7 cSt. It had a viscosity within the range. The API specific gravity of each crude oil product increased by 1.5-4.1 degrees. This increased API gravity corresponds to the API gravity of crude oil products in the range 21.7 to 22.95. The API share in this range is 110-117% of the API share of crude oil feeds.

FIG. 16 is a graph of oxygen content (“O ₂ ”) versus run time (“t”) of crude oil products in weight percentages for each catalyst system of Examples 8-11. Plots 172, 174, 176, and 178 each represent the oxygen content of the crude oil product obtained by contacting the crude oil feed with the catalyst system of Examples 8-11. Each crude product had an oxygen content of up to 16% of the crude feed. Each crude oil product had an oxygen content in the range of 0.0014 to 0.0015 grams per gram crude oil product during each test. As shown in FIG. 16, the oxygen content of the crude oil product remained relatively constant after 200 hours of contact time. The relatively constant oxygen content of the crude oil product shows that the selected organic oxygen compounds were reduced during contact. Since the TAN in these embodiments was also reduced, it can be inferred that at least some of the carboxyl group-containing organic oxygen compounds have been selectively reduced for non-carboxyl group-containing organic oxygen compounds.

In Example 11, crude oil feed at reaction conditions of 371 ° C. (700 ° F.), pressure of 6.9 MPa (1014.7 psi), and ratio of hydrogen to crude oil feed of 160 Nm ³ / m ³ (1000 SCFB) The decrease in water MCR content was 17.5 wt% based on the weight of the crude oil feed. At a temperature of 399 ° C. (750 ° F.), at the same pressure and the ratio of hydrogen to crude feed, the reduction in crude feed MCR content was 25.4 wt% based on the weight of the crude feed.

Crude feed in Example 9 at 371 ° C. (700 ° F.), pressure of 6.9 MPa (1014.7 psi), and reaction conditions of the ratio of hydrogen to crude feed of 160 Nm ³ / m ³ (1000 SCFB) The decrease in MCR content was 17.5 wt% based on the weight of the crude oil feed. At a temperature of 399 ° C. (750 ° F.), at the same pressure and the ratio of hydrogen to crude feed, the reduction in crude feed MCR content was 19 wt% based on the weight of the crude feed.

Increased reduction in crude feed MCR shows that the unbaked Group 6 and Group 10 metals catalyst promotes a decrease in MCR content at higher temperatures than the unbaked Group 6 and Group 9 metals catalyst.

These examples show that contacting one or more catalysts with a crude oil feed having a relatively high TAN (TAN of 0.8) produces a crude oil product having a relatively low net hydrogen uptake while maintaining the crude feed / final product mixture stability. . The selected properties of the crude product were within 20-30% of the same properties of the crude feed, while the selected crude product properties were up to 70% of the same properties of the crude feed.

Specifically, as shown in Table 4, each crude oil product with a net hydrogen uptake of up to 44 Nm ³ / m ³ (275 SCFB) by crude oil feed was prepared. These products had an average TAN of up to 4% of the crude feed, and an average total Ni / V content of up to 61% of the total Ni / V content of the crude feed, while maintaining three or more P-values for the crude feed. . The average residue content of each crude product was 88-90% of the residue content of the crude feed. The average VGO content of each crude product was 115-117% of the VGO content of the crude feed. While the viscosity of each crude product was at most 45% of the viscosity of the crude feed, the average API specific gravity of each crude product was 110-117% of the API specific gravity of the crude feed.

Example  12-14: average void of at least 180Å Diameter  Catalyst and crude oil feed with a pore size distribution of  Contact with minimum hydrogen consumption.

In Examples 12-14, each reaction apparatus (excluding the number and volume of contacting zones), each catalytic sulfidation method, each final product separation method, and each crude oil product analysis were the same as described in Example 5. . All catalysts were mixed with silicon carbide in the same volume ratio. The crude oil feed flowed from the top of each reactor to the bottom of the reactor. Silicon carbide was placed at the bottom of each reactor to serve as the bottom carrier. Each reactor had one contact area. After placing the catalyst / silicon carbide mixtures in the contacting zone of each reactor, silicon carbide was placed over the upper contacting zone to fill the dead space and serve as a preheating zone in each reactor. Each reactor was mounted in a Lindbergh furnace comprising a preheating zone, a contacting zone and three heating zones corresponding to the lower carrier. The crude oil feed was contacted with each catalyst in the presence of hydrogen gas.

A catalyst / silicon carbide mixture (40 cm ³ ) was placed on top of the silicon carbide to form a contact area. In Example 12, the catalyst was a vanadium catalyst as prepared in Example 2. In Example 13, the catalyst was a molybdenum catalyst as prepared in Example 3. In Example 14, the catalyst was a molybdenum / vanadium catalyst as prepared in Example 4.

The contact conditions for Examples 12-14 were as follows: the ratio of hydrogen to crude feed fed to the reactor was 160 Nm ³ / m ³ (1000 SCFB), LHSV was 1h ⁻¹ , and the pressure was 6.9 MPa. (1014.7 psi). The contact areas were heated incrementally to 343 ° C. (650 ° F.) over a period of time and held at 343 ° C. for 120 hours for a 360 hour total run time.

The final product was discharged from the reactor and separated as described in Example 5. For each catalyst system the net hydrogen consumption during contact was measured. In Example 12, the net hydrogen consumption was -10.7 Nm ³ / m ³ (-65 SCFB) and the TAN of the crude oil product was 6.75. In Example 13, the net hydrogen consumption was 2.2-3.0 Nm ³ / m ³ (13.9-18.7 SCFB) and the TAN of the crude product was in the range of 0.3-0.5. In Example 14, during the contact of the crude oil feed with the molybdenum / vanadium catalyst, the net hydrogen consumption was in the range of -0.05 Nm ³ / m ³ -0.6 Nm ³ / m ³ (-0.36 SCFB-4.0 SCFB) and the crude oil product TAN was in the range of 0.2-0.5.

From the net hydrogen consumption during contact, it was found that hydrogen was produced at a rate of 10.7 Nm ³ / m ³ (65 SCFB) during the contact of the crude oil feed with the vanadium catalyst. The generation of hydrogen during contacting makes it possible to use less hydrogen in the treatment process than the amount of hydrogen used in conventional treatment processes to improve the properties of lower crude oil. If less hydrogen is required during contacting, the processing cost of crude oil is reduced.

In addition, contacting the crude oil feed with the molybdenum / vanadium catalyst produced a crude oil product having a lower TAN than the TAN of the crude oil product made from the molybdenum catalyst alone.

Example  15-18. Crude oil contact with vanadium catalyst and additional catalysts.

Each reaction apparatus (excluding the number and volume of contacting zones), each catalytic sulfidation method, each final product separation method, and each crude oil product analysis were the same as described in Example 5. Unless stated otherwise, all catalysts are mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst. The crude oil feed flowed from the top of each reactor to the bottom of the reactor. Silicon carbide was placed at the bottom of each reactor to serve as the bottom carrier. Each reactor had a lower contact area and an upper contact area. After placing the catalyst / silicon carbide mixtures in the contacting zone of each reactor, silicon carbide was placed over the top contacting zone to fill the dead space and served as a preheating zone in each reactor. Each reactor was mounted in a Lindbergh furnace comprising a preheating zone, two contacting zones, and four heating zones corresponding to the lower carrier.

In each example, the vanadium catalyst was prepared as described in Example 2 and used with additional catalyst.

In Example 15, an additional catalyst / silicon carbide mixture (45 cm ³ ) was placed in the lower contacting zone, wherein the additional catalyst, which is a molybdenum catalyst, was prepared as described in Example 3. In the upper contact zone was placed a vanadium catalyst / silicon carbide mixture (15 cm ³ ).

In Example 16, an additional catalyst / silicon carbide mixture (30 cm ³ ) was placed in the lower contacting zone, wherein the additional catalyst, which is a molybdenum catalyst, was prepared as described in Example 3. In the upper contact area was placed a vanadium catalyst / silicon carbide mixture (30 cm ³ ).

In Example 17, an additional catalyst / silicone mixture (30 cm ³ ) was placed in the lower contacting zone, with the additional catalyst being a molybdenum / vanadium catalyst prepared as described in Example 4. In the upper contact area was placed a vanadium catalyst / silicon carbide mixture (30 cm ³ ).

18 embodiment, the bead ^{(30cm 3) Pyrex ® (Glass} Works Corporation, New York, USA) were placed in each contact area.

Crude oil (Santos Basin, Brazil) for Examples 15-18, summarized in Table 5 of FIG. 17, was fed to the top of the reactor. The crude oil feed flowed through the preheating zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. This crude feed was contacted with each catalyst in the presence of hydrogen gas. The contact conditions in each example were as follows: The ratio of hydrogen gas to crude oil feed to the reactor was 160 Nm ³ / m ³ (1000 SCFB) for the first 86 hours and 80 Nm ³ / for the remaining time. was m ³ (500 SCFB), LHSV was 1h ^- was ^1, and the pressure yiyeotda 6.9 MPa (1014.7 psi). The contact areas were heated incrementally to 343 ° C. (650 ° F.) over a period of time and held at 343 ° C. for a total run time of 1400 hours.

These embodiments combine crude oil in the presence of a hydrogen source by combining a Group 5 metal catalyst having a pore size distribution with an average pore diameter of 350 mm 3 with additional catalysts having a pore size distribution with an average pore diameter in the range of 250-300 mm 3. In contact with the feed, it is shown that a crude oil product is produced with varying properties for the same properties of the crude feed, while minor fluctuations in other properties of the crude product for the same properties of the crude feed. In addition, during the process, relatively little hydrogen consumption was observed with the crude oil feed.

Specifically, the crude oil product has a TAN of at most 15% of the TAN of the crude oil feed according to Examples 15-17, as shown in Table 5 of FIG. The crude oil product prepared in Examples 15-17 had up to 44% total Ni / V / Fe content, up to 50% oxygen content, and up to 75% viscosity with respect to the same properties of the crude feed. In addition, each of the crude oil products prepared in Examples 15-17 had an API gravity of 100-103% of the API gravity of the crude feed.

In contrast, crude oil products prepared under non-catalytic conditions (Example 18) produced products that exhibited an increase in viscosity and a decrease in API specific gravity with respect to the viscosity and API specific gravity of the crude feed. From the increase in viscosity and the decrease in API gravity, it can be inferred that coking and / or polymerization of the crude oil feed has begun.

Example  19. Various At LHSV  Crude oil feed of  contact.

The contacting systems and the contacting catalysts were the same as described in Example 6. Table 6 in FIG. 18 describes the characteristics of the crude oil feed. The contact conditions were as follows: the ratio of hydrogen gas to the crude oil feed to the reactor was 160 Nm ³ / m ³ (1000 SCFB), the pressure was 6.9 MPa (1014.7 psi), and the temperature of the contact zones was total. 371 ° C. (700 ° F.) for hours. Example 19 In, 1h ^-1 ~ 12 h increased to ^-1 and, 12 h for 48 hours during the period of time LHSV of contact ^- for 20.7 h and then was maintained at ^1, and a LHSV h ^-1 20.7 increases, 96 hours ^- it was kept at ^1.

In Example 19, crude oil was obtained to determine the TAN, viscosity, density, VGO content, residue content, heteroatomic content, and metals in the organic acid metal salt between the time of LHSV of 12 h ^{- 1} and the time of 20.7 h ^{- 1} . The product was analyzed. Average values for the properties of the crude oil products are shown in Table 6 of FIG. 18.

As shown in Table 6 of FIG. 18, the crude oil product in Example 19, whose API specific gravity was 104-110% of the API specific gravity of the crude oil feed, while lowered TAN and lowered in relation to the TAN and viscosity of the crude oil feed Had a viscosity. The weight ratio of MCR content to C ₅ asphaltene content was at least 1.5. MCR content and the combined amount of the C ₅ asphaltene content has been reduced in relation to the combined amount of the MCR content of the feed oil and C ₅ asphaltene content. C _5, rather than from a reduction in the combined ratio of the amount of the MCR content of the asphaltenes content and MCR content to C ₅ asphaltenes content of the component to form a coke you can try guessing that reduces the asphaltenes. The crude product also had a total content of potassium, sodium, zinc, and calcium of up to 60% of the total content of the same metals of the crude feed. The sulfur content of the crude product was 80-90% of the sulfur content of the crude feed.

Examples 6 and 19, LHSV is 1 h ^- the contact conditions for the production of crude product, as compared to the ^first processing step, having similar characteristics, the LHSV through the contacting zone is greater than the 10 h ^-1 Shows that you can control. The ability to selectively change the characteristics of the crude oil feed at liquid space velocities in excess of 10 h ⁻¹ allows the contact treatment process to be carried out in smaller vessels than can be obtained as a commodity. If the container is smaller in size, treatment of lower crude oil may be carried out at manufacturing sites (eg, offshore installations) with size constraints.

Example  20. Contact of crude oil at various contact temperatures.

The contacting system and the contacting catalysts were the same as described in Example 6. A crude oil feed having the properties listed in Table 7 of FIG. 19 was fed over the reactor and contacted with two catalysts in the presence of hydrogen in two contacting zones to produce a crude oil product. The two contact zones were operated at different temperatures.

The contact condition in the upper contact areas were as follows:. LHSV was 1 h ^- was a ^1, the temperature at the top contact area was 260 ℃ (500 ℉), the ratio of hydrogen to crude feed was 160 Nm ³ / m ³ (1000 SCFB) and pressure was 6.9 MPa (1014.7 psi).

The contact conditions in the bottom contact zone were as follows: LHSV was 1 h ^{- 1} , the temperature in the bottom contact zone was 315 ° C. (600 ° F.), and the ratio of hydrogen to crude oil feed was 160 Nm ^3. / m ³ (1000 SCFB) and pressure was 6.9 MPa (1014.7 psi).

The final product exited the lower contact zone and was introduced into the gas-liquid separator. In this gas phase-liquid separator, the final product was gas separated from the crude product. This crude product was analyzed periodically to determine the TAN and C ₅ asphaltene content.

Average values for the properties of the crude product obtained during the test run are listed in Table 7 of FIG. 19. The crude oil feed had a TAN of 9.3 and C ₅ per gram of crude oil feed. The asphaltene content was 0.055 grams. The average TAN of the crude product was 0.7 and the average C ₅ asphaltene content per gram of crude product was 0.039 grams. The C ₅ asphaltene content of the crude product is C ₅ of the crude product Up to 71% of the asphaltene content.

The total content of potassium and sodium in the crude product was at most 53% of the total content of the same metals in the crude feed. The TAN of the crude product was at most 10% of the TAN of the crude feed. During the contact, at least 15 P-values were maintained.

As shown in Examples 6 and 20, if the first (in this case, upper) contact temperature is 50 ° C. below the contact temperature of the second (in this case, bottom) region, C _{5 of the} crude oil feed There is a tendency to enhance the lowering of the C ₅ asphaltene content of crude oil products relative to asphaltene content.

In addition, temperature gap control was intensified to lower the content of metals in the organic acid metal salt. For example, the reduction in the total potassium and sodium content of the crude product from Example 20, crude oil from Example 6, showing a relatively constant crude feed / final product mixture stability as measured by P-value. It was enhanced compared to lowering the total potassium and sodium content of the product.

The use of low temperatures in the first contacting zone can lead to physical properties of high molecular weight compounds (eg, softness and / or viscous forces (eg, gums and / or tars)). C ₅ asphaltenes and / or organic acid metal salts)) which tend to form polymers and / or compounds having)). Removing these compounds at low temperatures allows them to be removed prior to plugging and coating the catalyst, thereby extending the life of the catalyst disposed after the first contacting zone and operating at higher temperatures. .

Example  21. Slurry  Contact of crude oil feed and catalyst in state

Bulk metal catalysts and / or catalysts of the present application (0.0001-5 grams or 0.02-4 grams of catalyst per 100 grams of crude oil feed), in some embodiments, are slurried with the crude oil feed under the following conditions: Can react for hours: hydrogen source for temperatures ranging from 85 to 425 ° C (185 to 797 ° F), pressures ranging from 0.5 to 10 MPa, and crude oil feeds ranging from 16 to 1600 Nm ³ / m ³ for a period of time Of rain. After a reaction time sufficient to produce the crude product, the crude product is separated from the catalyst and / or remaining crude feed using a separation device such as a filter and / or a centrifuge. For crude oil feeds, the TAN, iron, nickel, and / or vanadium content of the crude oil product may vary, and C ₅ The asphaltene content may be reduced.

In view of the present specification, other modifications and variations of the various aspects of the present invention will be apparent to those skilled in the art. Therefore, this specification is to be construed as illustrative only, and also for the purpose of informing the person skilled in the art the common way of carrying out the invention. The forms of the invention shown and described herein are to be taken as exemplary embodiments. With the aid of this specification of the present invention, the elements and materials may be substituted with the elements and materials shown and described herein, the elements and processes may be reversed, and certain features of the present invention. It will be apparent to those skilled in the art that these may be used independently. Changes may be made in the elements described herein without departing from the spirit and scope of the invention as set forth in the claims below.

Claims (29)

Combining the carrier with one or more metals to form a carrier / metal mixture, the carrier comprising theta alumina and having alpha alumina having an alpha alumina content of up to 0.1 grams per gram of carrier, according to ASTM specification D4282. Has a pore size distribution having a median pore diameter of at least 230 microns, wherein the one or more metals are one or more metals of Group 6 on the periodic table, one or more compounds of one or more metals on Group 6 on the periodic table, or mixtures thereof And, in addition, said compounding step comprising one or more metals of Group 5 on the periodic table, one or more compounds of one or more Group 5 metals, or mixtures thereof, and A heat treatment step of heat-treating the theta alumina carrier / metal mixture at a temperature of at least 400 ° C. The method of claim 1, wherein the median pore diameter of the pore size distribution is at most 500 mm 3. The process according to claim 1 or 2, wherein the pore volume of the pores in the pore size distribution is at least 0.3 cm ³ / g. 3. The process of claim 1, wherein the surface area of the catalyst is at least 60 m ² / g. The method of claim 1, wherein the one or more metals further comprise vanadium, cobalt, nickel, or mixtures thereof. The method of claim 1 or 2, wherein the one or more metals further comprise a carrier with one or more compounds of Group 15 and / or one or more Group 15 elements on the periodic table. . The method of claim 1, wherein the theta alumina content of the carrier is at least 0.1 grams per gram of carrier. 3. The method of claim 1 or 2, wherein the carrier further comprises delta alumina and / or gamma alumina as measured by x-ray diffraction. (a) one or more metals of group 6 of the periodic table, one or more compounds of one or more metals of group 6 of the periodic table, or mixtures thereof and further one or more metals of group 5 of the periodic table, of group 5 of the periodic table One or more compounds of one or more metals, or mixtures thereof, (b) a catalyst comprising a carrier material having a theta alumina content measured by x-ray diffraction of at least 0.1 grams per gram of carrier material, having alpha alumina having an alpha alumina content of at most 0.1 grams per carrier, ASTM specification D4282 A catalyst having a pore size distribution having a median pore diameter of at least 230 mm 3, as determined by. 10. The catalyst of claim 9 wherein at least one of the Group 5 metals is vanadium. The catalyst of claim 9 or 10, wherein the one or more Group 6 metals are molybdenum and / or tungsten. Process for preparing crude oil product comprising: A contacting step of contacting a crude oil feed having a total acid value (TAN) of at least 0.3 with at least one of the catalysts described in claim 9 to produce a final product comprising the crude oil product, the crude product at 25 ° C., 0.101 MPa Contacting the liquid mixture in a liquid phase; And Temperature in the range of 50-500 ° C., pressure in the range of 1-12 Mpa, and LHSV in the range of 0.1-30 h ⁻¹ (for the total volume of catalyst) such that the crude product has a TAN of up to 90% of the TAN of the crude feed. A control step for controlling the contact conditions in the ratio of the volume of liquid supplied per hour, wherein TAN is a control step obtained by ASTM specification D664. 13. The method of claim 12, wherein the TAN of the crude product is at most 50% of the TAN of the crude feed. 13. The method of claim 12, wherein the TAN of the crude product is in the range of 1-80% of the TAN of the crude feed. The process for producing a crude oil product according to claim 12, wherein the TAN of the crude oil product is in the range of 0.001 to 0.5. The method of claim 12, wherein the TAN of the crude oil feed is in the range of 0.3-20. The method of claim 12, wherein the crude oil feed is contacted in a contacting zone at or connected to an offshore facility. The method of claim 12, wherein the contacting step comprises contacting in the presence of a hydrogen source. The method of claim 12, wherein the method comprises combining the crude oil product with a crude oil equal to or different from the crude oil source to form a blend. The method of claim 12, further comprising the step of processing the crude oil product or combination to produce a transportation fuel, a heating fuel, a lubricating oil, or a chemical product. . 21. The method of claim 20, wherein said treating step comprises distilling said crude product or said blend into one or more distillates. 21. The process of claim 20, wherein said treating process comprises a hydrotreating step. delete delete delete delete delete delete delete

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